Polyurethane-based aqueous multicolor paint

ABSTRACT

An improved polyurethane-based water-in-water multicolor paint composition is provided having a disperse phase and a continuous phase which is characterized by an accelerated capacity to transfer from an applicator surface to a substrate surface during paint application. The disperse phase preferably is comprised of a water dispersible, inert film-forming, crosslinkable, polyurethane polymer system; hydroxy (lower alkyl) cellulose; quaternized water soluble cellulose ether; peptized clay and water. The continuous phase preferably is comprised of such a polyurethane polymer system, a water soluble, film-forming, crosslinkable, pressure-responsive contact adhesive, a peptized clay and water. Methods for preparing the paint are also provided.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of pending application Ser.No. 851,525 filed Mar. 16, 1992 now U.S. Pat. No. 5,199,980; which inturn is a continuation-in-part of application Ser. No. 694,311, filedMay 1, 1991, now U.S. Pat. No. 5,114,485 issued May 19, 1992; which inturn is a continuation-in-part of application Ser. No. 586,762, filedSep. 21, 1990, now U.S. Pat. No. 5,114,484 also issued May 19, 1992.

FIELD OF THE INVENTION

The present invention relates to an improved polyurethane-basedwater-in-water multicolor paint emulsion which can be applied rapidly asa surface coating with a paint roller, a brush or spray equipment.

BACKGROUND OF THE INVENTION

A multicolor paint is a composition which, when coated on a surface anddried, results in a coating that is characterized by dispersed discretevisibly discernible spots (or dots).

Water-in-water multicolor paints have been proposed (see, for example,Sellars et al. U.S. Pat. No. 3,950,283; Grasko U.S. Pat. No. 3,852,076and Zola U.S. Pat. No. 4,376,654) and are of commercial interestparticularly in view of the developing governmental interest inestablishing regulations limiting the quantity of organic volatilesemitted into the environment by a paint during application andsubsequent air drying. The states of California, New Jersey and NewYork, for example, have adopted regulations limiting paint emissions andmany other states reportedly will be adopting similar regulations.

The above-indicated related applications and patents provide new andvery useful water-in-water multicolor paints which overcome variousprior art problems. In such a new multicolor paint, there are aqueousdisperse phase color bodies that are characterized by having:

(a) a relatively high content of water dispersible, film-forming,crosslinkable polymer in association with a crosslinking agent,

(b) a relatively high structural integrity, and

(c) a capacity to form highly crosslinked, water insoluble, chemicalresistant, mar resistant and thermally stable coatings with a highdegree of hardness after paint application and drying.

These water-in-water multicolor paints are based upon crosslinkablecarboxylated polymers and crosslinkable polyurethane polymers.

When a painter manually applies such a water-based multicolor paintemulsion by transfer from an applicator (such as a brush, roller or thelike), there is a tendency for the painter to stroke the paint-carryingapplicator backwards and forwards repetitively over the substrate beingcoated (i.e., painted) in order to achieve the desired transfer andcoverage (with regard to both initial paint application and also paintcoating thickness). The more the stroking, the greater the possibilityof rupturing a portion of some of the disperse phase bodies that producethe multicolor effect in a dried coated paint. To minimize thepossibility of such undesirable rupturing, it would be desirable tosomehow effectuate a more rapid transfer of multicolor paint from anapplicator to a substrate. Associated further properties of early tack,quick stick and significant green strength would also be desirable.

The present invention provides a multicolor paint emulsion whichprovides such an accelerated paint transfer capability.

SUMMARY OF THE INVENTION

The present invention provides an improved water-in-water multicolorpaint which is characterized by a surprising accelerated capacity totransfer from an applicator surface to a substrate surface during paintapplication.

Surprisingly, the accelerated transfer rate of an inventive paint isachieved from an applicator, such as a brush, roller or the like, to asubstrate surface without adversely affecting the desirable multicolorpaint quality characteristics and especially without adversely affectingthe stability characteristics of the disperse phase color bodies. Thesestability characteristics include liquid multicolor paint storagestability, disperse phase body stability during paint application by anapplicator, and dried, coated paint stability following application.Also, the inventive paints retain the capacity for spray application, ifdesired.

In addition, a paint of this invention is characterized by having earlytack, quick stick and excellent green strength qualities.

The present inventive multicolor paint is achieved by introducing acontrolled amount of at least one member of a certain group ofwater-dispersible, crosslinkable, film-forming pressure-responsivecontact adhesives into a water-in-water multicolor paint of the typehaving a continuous phase and a disperse phase and wherein the dispersephase is comprised of bodies that incorporate a mixture of polymericmaterials comprised of:

(a) water dispersed, inert film-forming, crosslinkable polyurethanepolymer system selected from the group consisting of a polyurethanepolymer system, a carboxylated polymer system, and mixtures thereof, and

(b) hydroxy (lower alkyl) cellulose and/or alkali metal carboxyl (loweralkyl) cellulose.

Also, a pigment is optionally but preferably present in the dispersephase bodies and also in the continuous phase.

In the continuous phase, the water dispersed film-forming, crosslinkablepolymer system preferably comprises on a 100 weight percent totalpolymer solids basis about 75 to and including 100 weight percent of apolyurethane polymer system and correspondingly from and including 0 upto about 25 weight percent of a carboxylated polymer system.

In the present inventive multicolor paint, the continuous phase and thedisperse phase can generally be compounded and prepared as described inthe above-referenced parent patent application, U.S. Ser. No. 851,525,and also in concurrently filed U.S. Ser. No. 08/043,520 filed on evendate, except that a selected pressure-responsive contact adhesive isadded to and admixed with the continuous and/or the discontinuousphases, or preferably only with the continuous phase, as describedherein. The disclosure of these applications are incorporated herein byreference.

The resulting multicolor paint composition of this inventionsurprisingly and unexpectedly displays the capacity to transfer from anapplicator onto a substrate surface which is being painted usually farmore quickly than can be achieved with a corresponding multicolor paintwhich does not contain the pressure-responsive contact adhesive. Thesubstantially higher transfer rate not only results in relatively rapidtransfer of paint from applicator to substrate, but also results inproducing thicker paint substrate coatings in a shorter time frame thanis achievable with a corresponding multicolor paint which does notcontain the pressure-responsive contact adhesive. Better early tack,better quick stick and better green strengths are also observed.

A coating comprised of a multicolor paint composition of this inventioncharacteristically and surprisingly dries to a smooth, durable,non-tacky, highly water resistant layer.

The inventive multicolor paints have excellent stability characteristicsas indicated above. The dried coatings resulting from brush and rollerapplication display excellent surface and wear characteristics. Thedesirable qualities of the polyurethane-based, water-in-water multicolorpaint emulsions produced by the methods of U.S. Ser. No. 851,525 andSer. No. 08/043,520 are believed to be retained.

Other and further objects, aims, purposes, features, advantages,embodiments, and the like will be apparent to those skilled in the artfrom the present specification taken with the appended claims.

BRIEF DESCRIPTION OF THE DRAWING

In the drawing, a flow sheet is shown illustrating blending sequencessuitable for use in practicing the present invention.

DETAILED DESCRIPTION (a) Definitions

The term "water dispersed" or "water dispersible" as used herein withreference, for example, to a polyurethane polymer, a carboxylatedpolymer, a reactive curative, a crosslinking agent or like materialmeans that the material can form a water solution or a colloidalsuspension in water. However, to enhance the water dispersability ofsuch a material, and to increase the amount of the material which ispresent per unit of liquid volume in a water dispersed form,particularly in the disperse phase of a multicolor paint of thisinvention, the water is preferably admixed with a limited amount ofwater miscible organic liquid or cosolvent, such as hereinaftercharacterized and illustrated, wherein, for example, the polymer orother material, is at least as dispersible as in water.

The term "dispersed" (and its equivalent word forms such as"dispersible", "dispersability" and the like) is intended to includeboth colloidal and macrocolloidal suspensions, solutions, mixturesthereof, and the like. Preferably, such a polymer or other material ischaracterized by a capacity to disperse in the water-miscible organicsolvent (i.e., cosolvent) to an extent which is similar to that of thematerial dispersability in water alone. When a cosolvent is present, thequantity thereof is preferably less than about 8 weight percent based onthe total weight of the aqueous carrier liquid (or solvent or dispersingliquid) that is present in a given starting polymer dispersion orsolution particularly in order to comply with the foregoing regulationsregarding permissible volatiles.

The term "crosslinkable" as used herein with reference to a waterdispersed polyurethane system, a water dispersed carboxylated polymer,or the like, means that the polymer, after being applied to a surfacefrom an aqueous coating composition (particularly a multicolor paintcomposition of this invention) and allowed to form a film or coating,crosslinks (that is, thermosets or cures) and becomes water insolublethrough reaction. The crosslinking occurs preferably during the dryingwhich takes place after an aqueous coating composition of the polymer isapplied as a coating to a substrate surface and the aqueous carrier ofthe coating composition is evaporated. Also, the crosslinking preferablyoccurs at ambient temperatures and pressures, although heat maysometimes be used to accelerate the drying and the crosslinkingreaction.

The term "reactive curative" as used herein refers to any reagent orcombination of reagents which will react with a crosslinkablepolyurethane polymer (including a mixture of crosslinkable polyurethanepolymers) to produce a crosslinked polyurethane product when bothreagent(s) and the polyurethane polymer are first dispersed together inan aqueous starting dispersion and then are incorporated into a paintcomposition of this invention which is then coated upon a solidsubstrate and dried. As indicated herein, a reactive curative cansometimes be (that is, function as) a crosslinking agent for acrosslinkable carboxylated polymer.

The term "crosslinking agent" as used herein refers to an agent which,in dispersed combination with a crosslinkable carboxylated polymer in anaqueous paint composition of this invention, reacts with the polymer toproduce a crosslinked carboxylated polymeric product after the paintcomposition has been coated upon a solid substrate and dried.

The term "storage stability" as used herein with reference to amulticolor paint of this invention means that the paint passes the testprocedure of ASTM D-1849-80 which relates to the package stability ofpaint stored in a 1 quart or 1 liter container at 125°±2° F. (52°±1° C.)for 1 month or 2 months, respectively, with regard to consistency andsettling.

The term "structural integrity" as used herein in relation to amulticolor paint and the disperse phase bodies therein refers to theability of the disperse phase bodies therein to remain stable andsubstantially unchanged when subjected at ambient temperature andpressure to a shear mixing force exerted by a Cowles mixing bladeoperating at about 450 to about 500 rpm.

As used herein, the term "water resistance" as used herein withreference to a coated and dried film or coating produced from amulticolor paint of this invention refers to the test procedure of ASTMD-1308-79 with regard to both covered and open spot tests.

The term "paint" is used herein in the broad sense of a coloring andcoatable substance for spreading as a coating on a surface.

The term "inert film-forming" as used herein in reference to a givenpolymer or polymer system, particularly a polyurethane polymer systemwhich is employed in a multicolor paint of this invention, indicatesthat, when the given polymer or polymer system is deposited on asubstrate surface as a dried and substantially solvent-free coating,which may or may not be crosslinked, and which is comprisedsubstantially only of the given polymer or polymer system, that coatingis substantially inert. The term "inert" as used herein in this contexthas reference to the fact that such coating is a solid, has asubstantially non-tacky surface, and is substantially insoluble andresistant when transitionally contacted with water and common organicsolvents such as may be used generally in the paint art.

In contrast, the term "film-forming" as used herein in reference to agiven polymer or polymer system, particularly a pressure-responsive (orpressure-sensitive) contact adhesive which is employed in a multicolorpaint of this invention indicates that, when the given polymer orpolymer system is deposited on a substrate surface as a dried andsubstantially solvent-free coating which may or may not be crosslinkedand which is comprised substantially only of the given polymer orpolymer system, that coating is substantially tacky. The term "tacky" asused herein in this context has reference to the fact that such coatinghas a sticky surface to which solid objects contacted thereto adher.

(b) Starting Materials

The term "polyurethane" as used herein refers to a thermoplastic polymerwhich can be made crosslinkable (or thermosettable) and which isproduced by the reaction of a polyisocyanate (that is, an organiccompound containing at least two isocyanate (--N═C═O) groups permolecule) and a polyol (that is, a glycol compound containing at leasttwo hydroxyl (--OH) groups per molecule). The polymeric reaction productcontains repeating carbamate ester linkages (or urethane linkages) ofthe structure: ##STR1## When such linkages are present in a polymer, itis classified as a polyurethane herein.

Polyisocyanates also react with amines (that is, compounds which containat least one primary or secondary amino ##STR2## group per molecule(where R₁ is typically an alkyl, aryl, or like hydrocarbonaceousradical) in a similar fashion to produce a polymeric reaction productthat contains urea linkages: ##STR3## Polymers containing both urethaneand urea linkages are known as polyurethane ureas and such polyurethanepolymers can be used as starting polymers in the practice of thisinvention.

Either the starting polyisocyanate or the starting polyol can itselfhave an internal polymeric structure. Examples of suitable structuresinclude polyethers, polyesters, polyalkyls, polydimethylsiloxanes, andthe like. Commonly used isocyanates in polyurethane synthesis includetoluene dissocyanate (TDI) and methylene bis (p-phenyl isocyanate) or4,4'-dimethylmethane diisocyanate (MDI) although many other isocyanatesare available. Commonly used polyols include polyester and polyethers.

A polyurethane polymer can contain various functional (i.e., reactive)groups, such as one or more groups selected from the class consisting ofisocyanato, hydroxyl and amino (particularly primary or secondaryamino). Such functional groups are characteristically associated withpolyurethane polymers. However, in addition to, or apart from, suchfunctional groups, a polyurethane polymer can also contain otherfunctional groups such as carboxyl groups, sulfonic acid groups, and thelike, as those skilled in the art will appreciate.

Since the reaction of equimolar quantities of a macroglycol (or apolymeric polyol) and a diisocyanate typically results in a polymer withpoor physical properties, it is common to react the diisocyanate with alow molecular weight chain extender to produce a high molecular weighthard sequent which, when then reacted with a macroglycol, results in atwo-phase polyurethane microstructure with desirable physicalproperties. Diols and diamines are used for such chain extension.However, particularly because of dissolution and dispersion formingcapacity, diols are presently preferred for use as chain extenders inmaking such polyurethanes for use as starting materials in the practiceof this invention.

The water dispersed, inert film-forming, crosslinkable polyurethanepolymers and the aqueous polyurethane dispersions which are employed asstarting materials in the practice of this invention are generally knownto the prior art and do not as such constitute a part of the presentinvention. Aqueous crosslinkable polyurethane dispersions arecommercially available from a plurality of sources and are generallysuitable for use in the practice of this invention.

Although both aromatic and aliphatic aqueous crosslinkable polyurethanedispersions can be used, the aliphatic type is presently most preferredfor use in this invention because this type typically has better colorstability and more ultraviolet light (UV) resistance. Aromatic typesapparently have a tendency to yellow with age.

Various polymeric backbone types or classes can be used in a givenstarting polyurethane dispersion that is employed in this invention.Examples include:

A. Polyester type: Exhibits strong adhesion to difficult substrates.

B. Polyether type: Imparts softness, flexibility, hydrolysis resistanceand UV resistance to dried coatings.

C. Polycarbonate: Dried coatings display improved resistance toblocking, heat, ambient weather conditions, and resistance to chemicals.

D. Mixtures of different polymeric types which display combinations ofproperties can be prepared, for example, by using very high molecularweight polymer chains, or by introducing branching or crosslinking intoa polymer network.

Typically, though not necessarily, a starting aqueous polyurethanedispersion is formulated with an internal stabilization system.Polyurethane dispersions, as those skilled in the art will appreciate,may be classified according to the conventional internal stabilizationsystem used, such as: 1) anionic; 2) cationic or 3) nonionic. Of thesethree main systems, anionic polyurethane dispersions are presently mostpreferred. Nonionic types tend to be susceptible to water because of theinherent hydrophilic nature of the associated polymer and therefore arebelieved to be least desirable for use in the practice of thisinvention. Dispersion stabilization systems are known to thepolyurethane art and are not as such a part of the present invention.

Since the internal stabilization systems used in starting polyurethanedispersions particularly of the types that are commercially available donot adversely affect the method of preparation, the storage stability,the crosslinkability or the usability of product water-in-watermulticolor paints or this invention, so far as is now known, it isconvenient and now preferred to consider the internal stabilizationsystem as part of the starting water dispersed, film-forming,crosslinkable, polyurethane composition for purposes of weight percentcalculations and the like in preparing (and using) a product multicolorpaint of this invention.

Typical properties associated with starting crosslinkable polyurethanedispersions are illustrated in Table I below:

                                      TABLE I                                     __________________________________________________________________________    TYPICAL PROPERTIES ASSOCIATED WITH POLYURETHANE DISPERSIONS                                                            ALIPHATIC                                                                             ALIPHATIC                                  ALIPHATIC  AROMATIC                                                                              ALIPHATIC                                                                             POLYESTER                                                                             POLYESTER                                  POLYCARBONATE                                                                            POLYETHER                                                                             POLYETHER                                                                             (SOFT)  (HARD)                       __________________________________________________________________________    I. Dispersions                                                                Viscosity cps @ 25° C.                                                               100 GPS    50 GPS  20440 GPS                                                                             100 GPS 100 GPS                      pH              7.5        7.5     8.0     8.0     8.0                        II. Dried Coatings from                                                       Dispersions                                                                   Tensile strength (MPa)                                                                      40         10      40      40      45                           100% modulus (MPa)                                                                          20          2       9       2      35                           Extension at break (%)                                                                      290        1,000   700     1,000   250                          Konig hardness (secs)                                                                       75         15      78      13      90                           Est. N-methyl-2-pyrrolidone                                                                   9.5       0       1       2        12.5                       content (weight %)                                                            Solids %      30         35      40      40      30                           __________________________________________________________________________

Starting aqueous crosslinkable polyurethane dispersions can becrosslinked in the various ways known to the prior art. The moisturecure mechanism, however, is precluded for use in the aqueous polymersystem employed in the present invention. Suitable and presentlypreferred crosslinking polyurethane systems that are suitable for use inthe practice of the present invention can be cataloged as follows:

Type 1. One-component-precrosslinked: These polyurethane dispersions areformed by introducing tri- or higher poly-functionality into thecomponent polymeric molecular chains using suitable monomers, such asmultifunctional isocyanates, alcohols and/or amines. The resultingpolyurethane dispersions tend to require the presence in the liquidcarrier of a considerable proportion of an organic cosolvent, such as,for example, N-methyl-2-pyrrolidone, or the like. Crosslinking occursduring drying after coating without other additives being present.

Type 2. Two-component: These polyurethane dispersions are crosslinked bya multifunctional reactive curative which is preferably admixed with apolyurethane dispersion before it is incorporated into a composition ofthe invention and then is coated on a substrate. Crosslinking thenoccurs during coating and drying. Thus, crosslinking can be effectedwith reactive curatives which are water dispersible polyisocyanates. Apresently preferred class of such two-component polyurethane dispersionscomprises dispersed, anionically stabilized crosslinkable polyurethanescontaining incorporated functional carboxyl groups in combination with areactive curative. The carboxyl groups enhance formation of aqueousdispersions of the polyurethane polymer, and the dispersed carboxylatedpolyurethane polymer can be crosslinked with a wide range of acidicreactive curatives, including water dispersible polyisocyanates,multifunctional epoxy resins, multifunctional carbodiimides,polyfunctional aziridines, mixtures thereof, and the like.

Type 3. One-component-blocked: These polyurethane dispersions containblocked isocyanate groups which are chemically bound into thepolyurethane polymer chains and which are regenerated (or unblocked) atelevated temperatures such as at a predetermined temperature that can beutilized in a drying operation for a particular coating. The liberatedisocyanate groups then undergo the normal crosslinking reactions withurethane or urea groups on the originating or adjacent polymer chains.Such latent or blocked crosslinking sites are formed by reaction ofpendant or terminal isocyanate groups with blocking agents, whichpreferably are relatively low molecular weight compounds capable offorming thermally reversible bonds with isocyanate groups. When acoating containing such a polymer is heated to a certain temperature,the unblocking occurs preferably almost quantitatively, yielding bothfree isocyanate groups capable of crosslinking the polyurethane. Thefree blocking agent either remains, or preferably, migrates andevaporates. Heating is thus usually associated with the applicationand/or drying of polyurethane dispersions of this type. For presentpurposes, heating temperatures that are effective for initiatingcrosslinking below about 100° C. are preferred.

Crosslinking systems for aqueous crosslinkable polyurethanes are knownto the polyurethane prior art and are not as such part of the presentinvention. Since the polyurethane crosslinking systems used in startingpolyurethane dispersions particularly of the types that are commerciallyavailable do not adversely affect the method of preparation, the storagestability or the usability of product water-in-water multicolor paintsof this invention, so far as is now known, it is convenient and nowpreferred to consider the crosslinking system as part of the startingwater dispersed, inert film-forming, crosslinkable polyurethanecomposition for purposes of weight percent calculations and the like inpreparing (and using) a product multicolor paint of this invention.

For example, and preferably, a starting water disperse, film-forming,crosslinkable polyurethane polymer system composition used in thepractice of this invention can comprise on an estimated 100 weightpercent total solids basis about 75 to and including 100 weight percentof starting polyurethane polymer, from and including 0 up to about 25weight percent of starting reactive curative. Additionally, such systemmay optionally contain from and including up to about 15 weight percentof starting internal stabilization system. For convenience in practicingthis invention, such a polymer composition can be considered to be astarting water dispersed, inert film-forming, crosslinkable polyurethanepolymer system.

Also, the amount of water that is present in a given starting aqueouscrosslinkable polyurethane polymer system dispersion (includingsolution) is typically in the range of about 30 to about 65 weightpercent and is preferably in the range of about 50 to about 58 weightpercent (on a 100 weight percent total starting polyurethane dispersionbasis) with the amount of cosolvent when present ranging from andincluding 0 up to about 8 weight percent as indicated above, on the samebasis. Starting polyurethane dispersions containing other respectiveweight percentages of such components can also be employed, if desired.Also, as is typical of commercially available polyurethane dispersions,minor amounts of other components can sometimes be present. Mixtures ofdifferent inert film-forming polyurethane polymers can be employed, ifdesired.

Some examples of suitable commercially available starting aqueouscrosslinkable polyurethane dispersions and their properties are shown inTable II below.

                                      TABLE II                                    __________________________________________________________________________    EXEMPLARY STARTING AQUEOUS CROSSLINKABLE                                      COMMERCIALLY AVAILABLE POLYURETHANE DISPERSIONS                                                     Dispersion Composition                                                Polymer Type                                                                          % Polyurethane                                                                             organic                                                  (Aliphatic or                                                                         Solids in    solvent                                    I.D.                                                                             Manufacturer                                                                             Aromatic)                                                                             Dispersion                                                                            % water                                                                            %                                          __________________________________________________________________________       K. J. QUINN &                                                                 CO., INC.                                                                     SEABROOK, NH                                                                  Products:                                                                   1.                                                                              QW10       Aliphatic.sup.(1)                                                                     32                                                       2.                                                                              QW12       Aliphatic.sup.(1)                                                                     35                                                       3.                                                                              QW14       Aliphatic.sup.(1)                                                                     30      58.5 11.5                                        4.                                                                              QW16       Aliphatic.sup.(1)                                                                     40                                                       5.                                                                              QW18-1.sup.(3)                                                                           Aliphatic.sup.(1)                                                                     35      52   13.0                                          POLYVINYL                                                                     CHEMICAL INDUS                                                                WILMINGTON, MA                                                                Products:                                                                   6.                                                                              R-960      Aliphatic                                                                             33      48.5 18.5                                        7.                                                                              R-962      Aliphatic                                                                             34                                                       8.                                                                              R-966      Aliphatic                                                                             34                                                       9.                                                                              R-966      Aliphatic                                                                             33                                                      10.                                                                              R-967      Aliphatic                                                                             40      60   0                                             WITCO                                                                         HOUSTON, TX                                                                   Products:                                                                     W-232      Aliphatic                                                                             .sup.   30.sup.(2)                                                                    56.6 13.4                                          W-234      Aliphatic                                                                             .sup.   30.sup.(2)                                                                    57.7 12.3                                          W-240      Aliphatic                                                                             .sup.   30.sup.(2)                                                                    56.6 13.4                                          W-280      Aliphatic                                                                             .sup.   38  sup.(2)                                        W-290-H    Aliphatic                                                                             .sup.   62.sup.(2)                                                                    38   0                                             W-293      Aliphatic                                                                             .sup.   67.sup.(2)                                                                    33   0                                             W-3291     Aliphatic                                                                             .sup.   60.sup.(2)                                         W-3294     Aliphatic                                                                             .sup.   65.sup.(2)                                         SANCOR INDUST.                                                                LEOMINSTER, MA                                                                Products:                                                                     Sancure 815                                                                              Aliphatic                                                                             35      56.5  8.5                                       20.                                                                              822A       Aliphatic                                                                             30      55.6 13.4                                          847        Aliphatic                                                                             30      62.8  7.2                                          849        Aliphatic                                                                             35                                                         862        Aliphatic                                                                             35                                                         865        Aliphatic                                                                             35                                                         867        Aliphatic                                                                             40      60   0                                             878        Aliphatic                                                                             38      62   0                                             895        Aliphatic                                                                             35                                                         898        Aliphatic                                                                             32      60.2  7.8                                          899        Aliphatic                                                                             35      57.0  8.0                                       30.                                                                              1818       Aliphatic                                                                             35                                                         9500       Aliphatic                                                                             40                                                      __________________________________________________________________________     Table II footnotes:                                                           .sup.(1) Based upon information supplied by the indicated manufacturer,       the polyurethane contained in this dispersion is believed to be a             polyester.                                                                    .sup.(2) Based upon information supplied by the indicated manufacturer,       this dispersion is believed to contain an anionic internal stabilization      system.                                                                       .sup.(3) Based upon information supplied by the indicated manufacturer,       this dispersion is believed to contain a polyurethane polymer which has a     molecular weight in the range of about 5700 to about 7000.               

While it is presently preferred to make a multicolor paint of thisinvention using only one or more starting aqueous polyurethane polymersystem dispersions as the crosslinking polymer, useful multicolor paintsof this invention can also be prepared by using a polyurethane polymersystem dispersion in combination with a water dispersed, film-forming,crosslinkable, carboxylated polymer system as described herein.

Optionally but typically an organic crosslinking agent is used with acarboxylated polymer system. Also optionally but typically, acarboxylated polymer system comprises on a 100 weight percent totalsolids basis about 75 to and including 100 weight percent ofcarboxylated polymer and correspondingly from and including 0 to up toabout 25 weight percent of organic crosslinking agent. Also, the amountof water that is present in a given starting aqueous crosslinkablecarboxylated polymer system dispersion (including solution) is typicallyin the range of about 30 to about 65 weight percent and preferably is inthe range of about 50 to about 58 weight percent (on a 100 weightpercent total starting carboxylated polymer basis) with the amount ofcosolvent when present ranging from and including 0 up to about 8 weightpercent on the same basis. Other starting carboxylated polymerdispersions containing different respective weight percentages of suchcomponents can also be employed, if desired. Minor amounts of othercomponents may also be present.

The water dispersible, film-forming, crosslinkable, carboxylated polymersystems which are employed as polymeric starting materials in thepractice of this invention are not polyurethanes. Thus, such acrosslinkable carboxylated polymer system is preferably substantiallyfree from urethane linkages and urea linkages and also is preferablysubstantially free from functional groups selected from the classconsisting of hydroxyl, amino and isocyanato. Such carboxylated polymersare generally known in the prior art and do not as such constitute partof the present invention. Some examples of such polymers are shown inTable III below. Typically and preferably, a crosslinkable carboxylatedpolymer contains at least about 2 weight percent of carboxyl groups on a100 weight percent total carboxylated polymer weight basis, and morepreferably at least about 3 weight percent. Preferably, such a polymerdoes not contain more than about 7 weight percent of carboxyl groups(same basis).

                  TABLE III                                                       ______________________________________                                        CROSSLINKABLE, WATER SOLUBLE,                                                 FILM FORMING CARBOXYLATED POLYMERS                                            ID                  Trade Name/ Manufacturer/                                 No.  Chemical Name  Trade Mark  Source                                        ______________________________________                                         1.  Carboxylated Styrene                                                                         "Pliolite"  Goodyear                                           Acrylate Copolymer                                                                           7103 & 7104                                                2.  Carboxy-Modified                                                                             "Hycar" 26171                                                                             B. F. Goodrich                                     Acrylic                                                                   3.  Carboxy-Modified                                                                             "Hycar" 26137                                                                             B. F. Goodrich                                     Acrylic                                                                   4.  Carboxy-Modified                                                                             "Hycar" 26322                                                                             B. F. Goodrich                                     Acrylic                                                                   5.  Carboxy-Modified                                                                             "Hycar" 26083                                                                             B. F. Goodrich                                     Acrylic                                                                   6.  Carboxy-Modified                                                                             "Hycar" 26092                                                                             B. F. Goodrich                                     Acrylic                                                                   7.  Carboxy-Modified                                                                             "Hycar" 2671                                                                              B. F. Goodrich                                     Acrylic                                                                   8.  Carboxy-Modified                                                                             "Hycar" 26796                                                                             B. F. Goodrich                                     Acrylic                                                                   9.  Carboxy-Modified                                                                             "Hycar" 26084                                                                             B. F. Goodrich                                     Acrylic                                                                  10.  Carboxy-Modified                                                                             "Hycar" 26091                                                                             B. F. Goodrich                                     Acrylic                                                                  11.  Carboxy-Modified                                                                             "Hycar" 26288                                                                             B. F. Goodrich                                     Acrylic                                                                  12.  Carboxy-Modified                                                                             "Hycar" 26106                                                                             B. F. Goodrich                                     Acrylic                                                                  13.  Carboxy-Modified                                                                             "Hycar" 26172                                                                             B. F. Goodrich                                     Acrylic                                                                  14.  Carboxy-Modified                                                                             "Geon" 460x6                                                                              B. F. Goodrich                                     Vinyl Chloride                                                           15.  Carboxy-Modified                                                                             "Geon" 460x45                                                                             B. F. Goodrich                                     Vinyl Chloride                                                           16.  Carboxy-Modified                                                                             "Geon" 460x46                                                                             B. F. Goodrich                                     Vinyl Chloride                                                           17.  Carboxy-Modified                                                                             "Geon" 450x61                                                                             B. F. Goodrich                                     Vinylidene Copolymer                                                     18.  Carboxy-Modified                                                                             "Hycar" 1571                                                                              B. F. Goodrich                                     High Acrylonitrile                                                       19.  Carboxy-Modified                                                                             "Hycar"     B. F. Goodrich                                     Special Acrylonitrile                                                                        1570x55                                                   20.  Carboxy-Modified                                                                             "Hycar" 1572                                                                              B. F. Goodrich                                     Special Acrylonitrile                                                    21.  Carboxy-Modified                                                                             "Hycar" 1578                                                                              B. F. Goodrich                                     Special Acrylonitrile                                                    22.  Carboxy-Modified                                                                             "Goodrite"  B. F. Goodrich                                     Styrene Butadiene                                                                            257ox59                                                   23.  Carboxy-Modified                                                                             "Polyco" 2149c                                                                            Borden                                             Vinyl Acetate                                                            24.  Carboxy-Modified                                                                             "Polyco" 2142                                                                             Borden                                             Vinyl Acetate                                                            25.  Carboxy-Modified                                                                             "Darex" 5101                                                                              W. R. Grace                                        Styrene Butadiene                                                        26.  Carboxy-Modified                                                                             "Darex" 5261                                                                              W. R. Grace                                        Styrene Butadiene                                                        27.  Waterborne Aliphatic                                                                         "Sancure" 898                                                                             Sanncor Ind.                                       Urethane                                                                 28.  Waterborne Aliphatic                                                                         "Q-Thane"   K. J. Quinn & Co.                                  Urethane       QW-18                                                     ______________________________________                                    

As indicated above, a carboxylated styrene acrylate copolymer is themost preferred carboxylated polymer type for use in the practice of thepresent invention. For example, this product is available from Goodyearunder the trademark "Pliolite" with the associated product designationnumbers 7103 and 7104, and apparently contains about 65 percent byweight styrene and about 35 percent by weight of butyl acrylate and iscarboxylated to an extent sufficient to contain about 3 to 4 weightpercent carboxyl groups on a 100 weight percent total polymer weightbasis.

Such a carboxylated copolymer, for example, can be comprised of about 50to about 75 weight percent styrene and correspondingly about 25 to about50 weight percent of at least one (lower alkyl) acrylate monomer on atotal polymer weight basis. The acrylate monomer is preferably n-butylacrylate. Such a polymer is characterized by the feature that, after itsformation, it contains pendant carboxylic functional groups which arereactive with a crosslinking agent, such as a multifunctionalcarbodiimide or a polyfunctional aziridine, to produce a crosslinked,water insoluble product. The molecular weight of such a starting polymeris low enough to permit the polymer to be water dispersible.

In accordance with this invention, a starting aqueous or waterdispersable, inert film-forming crosslinkable polyurethane orpolyurethane polymer system is admixed with a starting aqueous or waterdispersable, film-forming, crosslinkable pressure-responsive (orpressure sensitive) contact adhesive. Such adhesives are known to theprior art and do not as such constitute a part of the present invention.

Such a pressure-responsive contact adhesive can be a polymer which has arelatively low glass transition temperature (T_(g)). Below the T_(g),the polymer has glass-like properties and above the T_(g) the polymerhas elastomeric properties. Presently preferred such adhesives includepolyurethane polymers and acrylic polymers. Other usable such adhesivesinclude isoprene rubber block copolymers, and vinyl acetate polymers,such as vinyl acetate polymers which are modified with an olefin such asethylene, or aqueous vinyl acetate polymer emulsions, or the like.However, such other adhesives may tend to suffer from certaindisadvantages, such as relatively poor color in a dried coating orrelatively poor ultraviolet light resistance. Aliphatic urethanepolymers, for example, such as those having a polyether backbone, appearto provide excellent green strength and long term durability and arepresently preferred.

Examples of preferred other (non-polyurethane) suitable waterdispersible, pressure-responsive, film-forming, crosslinkable contactadhesives include acrylic polymers, particularly acrylic polymerscontaining incorporated butyl acrylate, or acrylic polymers containingmethacrylates. Preferred such acrylic polymers are selfcrosslinking.

In general, these preferred adhesives adhere to a great variety ofsubstrates, provide clear film formation with high optical clarity,display great compatibility with multicolor paint compositions of thetype involved in this invention, are non-yellowing with age, and areultraviolet light resistant. These preferred adhesives can also becrosslinked which is presently preferred for adhesives used in thepractice of this invention. Crosslinking can be variously accomplished.For example, crosslinking of the adhesives used can be accomplishedthrough reaction with other polymeric materials present in a multicolorpaint formulation, such as with an inert film-forming polyurethanepolymer system, through reaction with a polyfunctional aziridine ormultifunctional carbodiimide, or the like.

Preferably, as in the case of a starting water dispersed, inertfilm-forming, crosslinkable polymer system, a starting waterdispersible, film-forming, crosslinkable pressure-responsive contactadhesive is preliminarily water dispersed or dissolved. Typically, sucha polymer dispersion contains from about 30 to about 65 weight percentof the adhesive polymer and preferably this amount is in the range ofabout 50 to about 60 weight percent. Such a dispersion can also containfrom and including 0 up to about 8 weight percent of cosolvent. Mixturesof different contact adhesives can be employed, if desired. Minoramounts of other components may sometimes be present.

Examples of suitable water dispersible, pressure-responsive,film-forming, crosslinkable contact adhesives are shown in Table IIIbelow.

                  TABLE III                                                       ______________________________________                                        Water Dispersable, Pressure-Responsive Adhesives                              Product   Company     Type                                                    ______________________________________                                        Elvare 1872                                                                             DuPont      Vinyl acetate co-modified                                                     with Ethylene                                           Elvare 1874                                                                             DuPont      Vinyl acetate co-modified                                                     with Ethylene                                           Elvare 1875                                                                             DuPont      Vinyl acetate co-modified                                                     with Ethylene                                           Elvare 1875HV                                                                           DuPont      Vinyl acetate co-modified                                                     with Ethylene                                           Elvare 1877                                                                             DuPont      Vinyl acetate co-modified                                                     with Ethylene                                           Gelva TS30                                                                              Monsanto    Vinyl acetate polymer                                                         emulsion                                                Gelva TS65                                                                              Monsanto    Vinyl acetate polymer                                                         emulsion                                                Gelva TS85                                                                              Monsanto    Vinyl acetate polymer                                                         emulsion                                                Gelva S-51                                                                              Monsanto    Vinyl acetate polymer                                                         emulsion                                                Gelva S-52                                                                              Monsanto    Vinyl acetate polymer                                                         emulsion                                                Gelva S-55                                                                              Monsanto    Vinyl acetate polymer                                                         emulsion                                                Gelva S-77                                                                              Monsanto    Vinyl acetate polymer                                                         emulsion                                                Gelva S-98                                                                              Monsanto    Vinyl acetate polymer                                                         emulsion                                                Gelva TS-70                                                                             Monsanto    Vinyl acetate polymer                                                         emulsion                                                UCARLATEX Union Carbide                                                                             Acrylic polymer emulsion                                173                                                                           UCARLATEX Union Carbide                                                                             Acrylic polymer emulsion                                174                                                                           UCARLATEX Union Carbide                                                                             Acrylic polymer emulsion                                175                                                                           Hycar 26171                                                                             B. F. Goodrich                                                                            Acrylic polymer emulsion                                Hycar 26146                                                                             B. F. Goodrich                                                                            Acrylic polymer emulsion                                Hycar 2600                                                                              B. F. Goodrich                                                                            Acrylic polymer emulsion                                x 207                                                                         Hycar 2600                                                                              B. F. Goodrich                                                                            Acrylic polymer emulsion                                x 222                                                                         Robond P520                                                                             Rotim & Haas                                                                              Acrylic emulsion                                                              (butyl acrylate)                                        Robond P583D                                                                            Rotim & Haas                                                                              Acrylic emulsion                                                              (butyl acrylate)                                        Luhydran  BASF        Methacrylate dispersion                                 A-848-S               (modifies the (T.sub.g)                                                       increases the glass                                                           transition temperature                                                        at room temperature)                                    LQW10-207 K. J. Quinn Aliphatic urethane                                                            (backbone polyether)                                    ______________________________________                                    

While a multicolor paint of this invention as described herein canincorporate into each of the dispersed phase and the continuous phase, amixture of both (a) one or more starting aqueous dispersions of one orboth of the inert film-forming crosslinking polymer systems, and (b) oneor more aqueous dispersions of film-forming pressure-responsive contactadhesives, one type of useful and presently multicolor paint of thisinvention can be prepared by compounding into the continuous phase amixture of a polyurethane polymer system with such an adhesive, and bycompounding into the disperse or discontinuous phase only an inertfilm-forming carboxylated polymer system. The advantage of such a painttype is that the disperse phase then incorporates polymers which are ofrelatively lower cost than the polymers incorporated into the continuousphase, yet the product multicolor paint retains the indicated desirablecharacteristics.

Various other materials are also employed in formulating paintcompositions of this invention.

Hydroxy (lower alkyl) cellulose materials are employed in the practiceof this invention as starting materials and are generally known in theprior art. As used herein, the term "lower alkyl" generally refers to analkyl moiety containing from (and including) one through four carbonatoms. Presently most preferred for use in this invention is a cellulosetype additive material such as hydroxyethyl cellulose. A suitable formof such material is available commercially under the trademark"Cellosize" from the Union Carbide Chemicals Company. Such a material isa water-soluble cellulose ether which is believed to be interactive withpeptized water swellable clays in aqueous gels, thereby aiding in theformation and maintenance of the disperse phase bodies in a multicolorpaint composition of this invention. Hydroxypropyl cellulose is alsouseful, for example.

The alkali metal carboxy (lower alkyl) cellulose materials employed inthe practice of this invention as starting materials are also generallyknown to the prior art. Presently, a most preferred alkali metal carboxy(lower alkyl) cellulose is sodium carboxy methyl cellulose. One suchmaterial that is available commercially is "CMC-7-7H3SF" from theAqualon Company.

The cationic quaternized cellulose materials employed in the practice ofthis invention as starting materials are also generally known in theprior art. These polymeric materials are available commercially, forexample, from Union Carbide Corporation under the trademark "Polymer JR"or "UCARE Polymer" in a variety of viscosity grades. These materials arealso known as, and designated by, the CTFA (that is, the Cosmetic,Toiletry and Fragrance Association, Inc.) as "Polyquaternium-10" whichis defined as a polymeric quaternary ammonium salt of hydroxyethylcellulose that has been reacted with a trimethyl ammonium substitutedepoxide. Such a water-soluble cellulose ether is theorized to beinteractive with at least one other component present in the dispersephase bodies employed in a paint of the present invention; however, thenature of this interreaction is not now known.

The pigment employed in the practice of this invention as a startingmaterial can be selected from among the various pigments known in theprior art. Preferably, the pigment is in the form of dispersibleparticles having ultimate particle sizes in the submicron range. Thepigment should preferably also be substantially insoluble in water or inorganic solvents. While a pigment should have a positive colorant value,it can be organic, inorganic, or a mixture of organic and inorganicmaterials. If desired, as those skilled in the art will appreciate, thepigment can be prepared preliminarily as a slurry, dispersion, or thelike in water and/or organic liquid for purposes of simple mechanicalblendability. Particulate metals can be used as pigments.

Presently preferred pigments include, for example, titanium dioxide;lamp black; carbon black; bone black; phthalocyanine blue;phthalocyanine green; various organic and inorganic yellow pigments,such as, for example, D & C yellows including quinoline yellow, yellowiron oxide, and the like; various organic and inorganic red pigments,such as, for example, D & C reds including quinacridone red and red ironoxide, respectively, and the like; etc.

The dispersible, water swellable clays employed in the practice of thisinvention can be selected from among the various known such clays, bothnatural and synthetic. Preferably, the clay selected is a silicate whichhas an ultimate particle size in the submicron range. Examples ofsuitable clays include synthetic silicate clays resembling hectoriteand/or saponite, montmorillonite, beidellite, nontronite, sauconite,stevensite, smectite and other inorganic minerals which arecharacterized by a tendency to swell by absorbing water between adjacentcrystal layers, and to split into fragments capable of forming colloidaldispersions. A presently most preferred silicate clay is a syntheticsodium magnesium lithium silicate hectorite-type clay. This material isobtainable commercially from Waverly Mineral Products of Balacynwyd, Pa.which is a subsidiary of La Porte Inc. of the United Kingdom under thetrademark designation "Laponite" RD or RDS. Other suitable hectoriteclays are available commercially from the R. T. Vanderbilt Company underthe trademark "Veegum T", or from the Baroid Div., National Lead Companyunder the trademark "Macaloid" .

The foregoing clays are employed in the practice of this invention incombination with a water soluble peptizing agent. Such an agent inducesthe clay to form a stable colloidal aqueous dispersion. Use of such anagent is conventional with such clays. Examples of known water solublepeptizing agents include ammonium hydroxide, hydrogen peroxide, sodiumcarbonate, sodium citrate, sodium hydroxide, sodium oxalate, sodiumsilicate, sodium tripolyphosphate, sodium hexametaphosphate, tetrasodiumpyrophosphate, and the like. The last named peptizing agent is presentlypreferred for use in the practice for this invention.

When a Type 2 (two component) polyurethane dispersion is employed, areactive curative is present, as indicated above, to producecrosslinking. The reactive curative can be and preferably is a waterdispersible polyisocyanate. Suitable polyisocyanates are availablecommercially. Presently, a most preferred polyisocyanate is an aliphaticpolyisocyanate that has a molecular weight in the range of about 260 toabout 264.

When the polyurethane polymer of a Type 2 dispersion contains carboxylgroups to enhance water dispersability (as is known in the art ofpolyurethanes), the reactive curative can (in addition to apolyisocyanate) include a wider range of reagents, such asmultifunctional epoxy resins, multifunctional carbodiimides,polyfunctional aziridines, mixtures thereof, and the like.

Suitable multifunctional epoxy resins are available commercially.. Sucha resin can contain an incorporated amine for imparting water solubilityor disperability thereto, a presently needed property. One suitable andpresently preferred multifunctional epoxy resin is availablecommercially as "EPI-REZ WD-510" from the Rhone-Poulenc Company.

The multifunctional carbodiimides and the polyfunctional aziridines canbe the same agents as those used to crosslink a crosslinkablecarboxylated polymer as described herein.

The multicolor paint compositions of this invention contain, when acrosslinkable carboxylated polymer is present in either the dispersephase or the continuous phase thereof, a crosslinking agent which iseffective for crosslinking the carboxylated crosslinkable polymersinvolved. Preferably, the crosslinking agent is present in the samephase as that in which the crosslinkable carboxylated polymer ispresent. Suitable water dispersible crosslinking agents for use in thisinvention which can interreact with such carboxylated polymers atambient temperatures and pressures are preferably polyfunctionalaziridines and multifunctional carbodiimides (the latter class beingpresently preferred). Such materials are known in the prior art and areavailable commercially.

Carbodiimides (sometimes also called cyanamides) are a well-known classof organic compounds having the general structure:

    R.sub.1 -N═C═N-R.sub.2

where R₁ and R₂ are each an organic moiety. Carbodiimides crosslink withcarboxylic acid groups to form N-acyl ureas.

A presently preferred carbodiimide is available commercially from UnionCarbide under the trademark "UCARLNK XL-25 SE" which is designated as"multifunctional" and is designed for use as a low-temperaturecrosslinking agent for polymers such as carboxylated polymers.

Aziridines are organic compounds based on the ring structure: ##STR4## Apresently preferred crosslinking polyfunctional aziridine is "ZAMA-7"which is designated "polyfunctional" and is available commercially fromHoechst Celanese and also from Virginia Chemicals. This material also isdesigned for use as a low-temperature crosslinking agent for polymerssuch as carboxylated polymers.

As indicated above, the disperse phase bodies and the pigmented,unpigmented or colored continuous phase of this invention preferablyeach incorporate a water-miscible organic liquid as a cosolvent incombination with the water employed therein. Any convenient watermiscible organic liquid can be used, but presently preferred liquidsinclude ester alcohols, such as a material available commercially fromEastman Kodak Company under the trademark "Texanol"; glycol ethers, suchas diethylene glycol butyl ether, which is available from Union CarbideCorporation under the trademark "Butyl Carbitol"; and ethylene glycolbutyl ether, which is available from Union Carbide Corporation under thetrademark "Butyl Cellosolve"; heterocyclics, such asN-methyl-2-pyrrolidone; and the like. N-Pyrrolidine which is availablefrom GAF can also be used.

As can be seen from the foregoing description, in a multicolorwater-in-water paint of this invention, a water dispersed polyurethanepolymer system is preferably a Type 1, Type 2 or Type 3 with regard toits crosslinkability. Thus, in the case of a Type 1 polymer system, thewater dispersed polyurethane polymer system preferably comprises, on a100 weight percent total crosslinkable polymer solids basis, a waterdispersed polyurethane polymer and this polymer is:

(a) comprised of polymer molecules produced by polymerizing mainlymonomers which are characterized by containing at least three functionalgroups per monomer, and wherein said functional groups are selected fromthe group consisting of isocyanato, hydroxyl, primary amino andsecondary amino, and

(b) self crosslinkable when dried from an aqueous dispersion at ambienttemperatures.

In the case of a Type 2 polymer system, the water dispersed polyurethanepolymer system:

(a) preferably comprises on a 100 weight percent total crosslinkablepolymer solids basis, a mixture of at least about 75 weight percent of awater dispersed reactable polyurethane polymer with the balance up to100 weight percent thereof being a water dispersed reactive curativewhich is reactive with such polymer, and

(b) is crosslinkable when dried from an aqueous dispersion at roomtemperature.

In one Type 2 preference, the reactive curative comprises a waterdispersible polyisocyanate.

In another Type 2 preference, the reactable polyurethane polymer hasunreacted functional groups and at least some thereof are carboxylgroups and the remainder thereof are selected from the group consistingof isocyanato, hydroxyl, primary amino and secondary amino. Here, thewater dispersible reactive curative is preferably selected from thegroup consisting of water dispersible polyisocyanates, water dispersiblemultifunctional epoxy resins, water dispersible multifunctionalcarbodiimides and water dispersible polyfunctional aziridines.

In the case of a Type 3 polymer system, the water dispersed polyurethanepolymer system preferably comprises (on a 100 weight percent totalcrosslinkable polymer solids basis) a water dispersed polyurethanepolymer; and the polymer is:

(a) characterized by containing a plurality of terminal isocyanatogroups per molecule which are each blocked by an associated blockingagent, and the blocking agent is thermally released from substantiallyall its associated respective isocyanato groups at a temperature in therange of about 50° to about 150° C., and

(b) crosslinkable when dried from an aqueous dispersion, and theblocking agent is thermally released at that temperature.

In a multicolor paint of this invention, the polyurethane polymer systemis preferably maintained in a water dispersed state by means of aninternal stabilization system that is anionic, as indicated above, andthat is also incorporated into a starting water dispersed polyurethanepolymer system.

(c) Preparation of Blending Compositions

In preparing a multicolor paint composition of this invention, it isconvenient and presently preferred to prepare four compositionsinitially, which are designated respectively as "Composition A","Composition B", "Composition C" and "Composition D", each of which isdescribed below.

COMPOSITION A

Composition A is conveniently prepared by preliminarily dissolving thehydroxy (lower alkyl) cellulose (presently preferred) and/or the alkalimetal carboxy (lower alkyl) cellulose in a starting water dispersed,inert film-forming crosslinkable polymer system. The carrier liquid ispreferably a water/cosolvent mixture. Thereafter, the pigment when usedis conveniently dispersed in the resulting mixed dispersion.

A non-polyurethane carboxylated polymer system (as described above) canbe alternatively, or additionally but optionally, present with apolyurethane polymer system, in a Composition A in dispersed (preferablydissolved) form. The total amount of water dispersed, film-forming,crosslinkable polymer system employed in a Composition A falls in therange of about 10 to about 45 weight percent (based on 100 weightpercent total of a Composition A). However, the amount individually ofeither polymer system that is employed can range from and including 0 upto about 45 weight percent (same basis) in a Composition A. The amountof crosslinking agent added when this carboxylated polymer is used ispreferably at least sufficient to crosslink this polymer when thepolymer and the crosslinking agent are dried from an aqueous dispersionat room temperature.

Composition A optionally may also contain a water dispersable,film-forming, crosslinkable, pressure-responsive adhesive as describedherein. When present in Composition A, such an adhesive is believed toimprove the capability for a multicolor paint composition of thisinvention to bond to various substrates of widely differentcompositions. In general, it is now preferred to add less than about 10weight percent (based on total weight of Composition A) and morepreferably less than about 5 weight percent (same basis) of such anadhesive.

Preferably, the adhesive used is water soluble and is a member of theclass consisting of acrylic polymers having a butyl acrylate backboneand aliphatic polyurethane polymers having a polyether backbone and morepreferably a low T_(g). The term "acrylic polymer" as used hereinincludes polymers containing at least about 50 weight percent (on atotal polymer weight basis) of an acrylic or acrylate polymerizedmonomer.

Typically, but preferably, Composition A also includes various optionaladditives of the type and in the respective amounts conventionally usedin paint formulations, such as plasticizers, bonding agents,anti-foaming agents, wetting agents, fungicides, neutralizers, and/orthe like. It can be regarded as a feature of the present invention thatsuch additives can be used effectively in a multicolor paint of thisinvention and can achieve their respective known effects withoutadversely affecting such desirable paint properties as formulatability,storage stability, applied dried coating water resistance, dispersephase body structural integrity, or the like.

Examples of suitable plasticizers preferably include monomericplasticizers, such as phthalates like dibutyl phthalate, diisodecylphthalate, dioctyl phthalate, tricresyl phosphate, butyl benzylphthalate, and the like. Other suitable monomeric plasticizers can beselected from among the adipates, sebacates, glycolates, castor oils,and the like.

Examples of suitable bonding agents include epoxidized siloxanes, suchas a glycidyl silane like glycidoxy trimethoxy silane, and the like.

Examples of suitable anti-foaming agents include the materials availablecommercially from Henkel under the trademarks "Foamaster VL", "Dehydran1293", "Nopco NXZ", and the like.

Examples of suitable wetting agents include polycarboxylic acid saltssuch as are available from Rohm and Haas under the trademark "Tamol" 165and also the materials that are available commercially from Rohm andHaas under the trademark "Triton", especially the products CF10 andX100.

Colloidal silicas are available commercially from various manufacturersand function as optional flattening agents in paints of this invention.

Various organofunctional silanes and siloxanes are availablecommercially from various manufacturers and function as propertyimprovers. For example, silanol groups (SiOH) react with organicscontaining hydroxyl groups and improve a dried coating's waterresistance, weathering resistance, and electrical resistance.

The preferred compositional characteristics of a Composition A are shownin Table IV. When, as in Table IV, a composition can contain both areactive curative (which is in a polyurethane polymer system forpurposes of crosslinking) and a crosslinking agent, it will beunderstood that the amount of crosslinking agent specified is forpurposes of causing a carboxylated polymer (not a polyurethane) that ispresent to crosslink and vice versa with respect to the amount of thereactive curative (if separately calculated) for a polyurethane polymer.However, the amount of reactive curative employed in relation to a givenpolyurethane polymer is usually not separately shown.

                  TABLE IV                                                        ______________________________________                                        COMPOSITION A                                                                                    Weight Percent                                                                100% Basis.sup.(1)                                         Ident.                   Broad     Preferred                                  No.   Component          (about)   (about)                                    ______________________________________                                        1     Inert film-forming polymer                                                                       10-40%    14-35%                                           system                                                                  1a    Polyurethane polymer system                                                                      (0-40%)    (0-14%)                                   1b    Carboxylated polymer system                                                                      (0-40%)    (0-35%)                                   2     Crosslinking agent (0-10%)   (2.5-3%)                                   3     Pressure-responsive adhesive                                                                     0-10%     0-5%                                       4     Hydroxy (alkyl) cellulose                                                                        0.5-2%    0.75-1.25%                                       and/or alk. metal carboxyl                                                    (alkyl cellulose)                                                       5     Water              20-80%    40-65%                                     6     Organic cosolvent  0-15%     4.0-8.0%                                   7     Pigment            0-30%      5-20%                                     8     Monomeric plasticizer                                                                            0-3%      1-2%                                       9     Bonding agent       0-0.5%   0.10-0.3%                                  10    Anti-foaming agent  0-0.5%   0.10-0.3%                                  11    Wetting agent       0-1.0%   0.25-0.75%                                       (Total)            (100.0)   (100.0)                                    ______________________________________                                         Table IV Footnote:                                                            .sup.(1) Weight ranges enclosed in parentheses are not included in the 10     weight percent total composition basis since such ranges are associated       with (i.e., are incorporated with) item 1 (the polymer system).          

Characteristically, Composition A preferably has a viscosity that isbelieved to be in the range of about 15,000 cps to about 25,000 cps(centipoises) measured with a Brookfield viscometer at 25° C. operatingat 20 rpm spindle speed with a No. 4 spindle.

Preferably, the water employed in the practice of this invention isfiltered and is either deionized or distilled A present preference is toemploy a water and organic water-miscible cosolvent medium comprised ofabout 85 to about 90 weight percent water with the balance up to 100weight percent on a total solvent composition weight basis thereof beingthe cosolvent (as characterized above).

COMPOSITION B

Composition B is prepared by dissolving the quaternized cellulose etherin water. The preferred compositional characteristics of Composition Bare identified in Table V below:

                  TABLE V                                                         ______________________________________                                        COMPOSITION B                                                                                    Weight Percent                                                                100% Basis                                                 Ident.                   Broad     Preferred                                  No.   Component          (about)   (about)                                    ______________________________________                                        1     Water                55-99.5 98%                                        2     Quaternized cellulose ether                                                                      0.5-5      2%                                              (Total)            (100.0)    (100.0)                                   ______________________________________                                    

Characteristically, Composition B preferably has a viscosity that isbelieved to be in the range of about 50,000 to about 55,000 centipoisesmeasured at 25° C. with a Brookfield viscometer using a No. 4 spindleoperating at a spindle speed of 20 rpm.

COMPOSITION C

Composition C is prepared by dissolving a peptizing agent in water andthen dispersing a water swellable clay in the resulting solution. Ingeneral, the respective amount employed of each material is such thatthe resulting aqueous system forms a gel. As indicated above, thepresently most preferred clay is a synthetic sodium magnesium lithiumhectorite clay, and the presently most preferred peptizing agent istetrasodium pyrophosphate.

Composition C is preferably characterized as shown in Table VI:

                  TABLE VI                                                        ______________________________________                                        COMPOSITION C                                                                                  Weight Percent                                                                100% Basis                                                   Ident.                 Broad    Preferred                                     No.      Component     (about)  (about)                                       ______________________________________                                        1        Water         88-95%   89.4%                                         2        Clay           5-10%   9.5%                                          3        Peptizing Agent                                                                             0.5-2%   1.1%                                                   (Total)       (100.0)  (100.0)                                       ______________________________________                                    

Characteristically, Composition C preferably has a viscosity that isbelieved to be in the range of about 80,000 to about 90,000 cps measuredat 25° C. with a Brookfield viscometer operating with a No. 4 spindle ata spindle speed of 20 rpm. Characteristically also, Composition C is athixotropic gel.

COMPOSITION D

Composition D is conveniently and preferably prepared by dissolving thewater dispersible, inert film-forming, crosslinkable polyurethanepolymer, the water dispersible, film-forming, pressure-responsivecrosslinkable adhesive, and other components such as identified in TableVII below in a water/cosolvent mixture. Thereafter, a peptizing agent isdissolved in water, and a water swellable clay is dispersed in theresulting solution which is added to the water/cosolvent mixture. Thedispersed, inert film-forming polymer system, as in the case ofComposition A, is selected from the group consisting of a polyurethanepolymer system, a carboxylated polymer system, and mixtures thereof.However, in the case of Composition D, the dispersed polymer systemcomprises on a 100 weight percent total dispersed polymer solids basisabout 75 to and including 100 weight percent of the polyurethane polymersystem, and correspondingly, from and including 0 up to about 25 weightpercent of the carboxylated polymer system. Preferably, this polymersystem is comprised of the polyurethane polymer system.

The same adhesive preferences apply here that were expressed above inreference to Composition A; however, in general, it is now preferred toadd to Composition D up to about 30 weight percent (on a totalComposition D weight basis) of the pressure-responsive adhesive, and,more preferably about 5 to about 25%.

Composition D is preferably characterized as shown in Table VIII:

                  TABLE VIII                                                      ______________________________________                                        COMPOSITION D                                                                                Weight Percent                                                                100% Basis.sup.(1)                                                                              Presently                                    ID    Component      Broad Range Preferred                                    ______________________________________                                        1     Crosslinkable  5-40%       10-30                                              Polymer System                                                          1a    Polyurethane   (5-40%)     (15-30%)                                           Polymer System                                                          1b    Carboxylated     (0-8.75%)   (0-7.5%)                                         Polymer System                                                          2     Crosslinking agent                                                                           (0-3%)      (0-2%)                                       3     Pressure-responsive                                                                          0-30%        5-25%                                             adhesive                                                                4     Clay           1.5-5%      2-4%                                         5     Peptizing agent                                                                              0.1-0.8%    0.15-0.2%                                    6     Anti-foaming agent                                                                             0-0.25%    0.1-0.15%                                   7     Wetting agent    0-0.25%    0.1-0.15%                                   8     Colloidal silica                                                                             0-5%        0.5-3%                                       9     Organofunctional                                                                               0-0.25%   0.04-0.2%                                          silane                                                                  10    Pigment        0-30%        5-20%                                       11    Organic cosolvent                                                                            0-15%       4-8%                                         12    Water          30-70%      40-65%                                             TOTAL          (100.00)    (100.00)                                     ______________________________________                                         Table VIII Footnote:                                                          .sup.(1) Weight ranges enclosed in parentheses are not included in the 10     weight percent total composition basis since such ranges are associated       with (i.e., are incorporated with) item 1 (the polymer system).          

Characteristically, Composition D has a preferred viscosity that isbelieved to be in the range of about 500 to about 5,000 centipoisesmeasured at 25° C. with a Brookfield viscometer using a No. 4 spindle ata spindle speed of 20 rpm.

(d) Preferred Blending Procedures

In a water-in-water multicolor paint of this invention, it is nowpreferred that the total amount of water dispersed, film-forming,crosslinkable, pressure-responsive contact adhesive employed in both thediscontinuous and continuous phases fall in the range of about 5 toabout 30 weight percent on a 100 weight percent total paint compositionbasis, and, more preferably, in the range of about 12 to about 25 weightpercent. The discontinuous phase preferably contains no more than about10 weight percent, and the continuous phase no more than about 30 weightpercent (same basis). However, at least one of either the discontinuousaqueous phase or the continuous aqueous phase contains such adhesive (inan amount to equal an amount that is in the total weight percent rangeindicated). As indicated, the adhesive which is preferably selected fromthe group consisting of polyurethanes and acrylic polymers. Preferably,the adhesive is always present, at least in the continuous phase.

Compositions A, B and C are usable in various combinations to preparedisperse phase compositions which are then broken up under mixing shearforce to form disperse phase bodies in a continuous phase comprised ofComposition D.

Referring to the flow sheet in the appended drawing, which is submittedto be self-explanatory, it is seen that a Composition A is blended witheither Composition B or Composition C, and preferably with both suchCompositions B and C, to prepare a disperse phase composition which ishomogeneous. The preferred weight ratios of Composition A to suchCompositions B and/or C, as the case may be, and also the preferredviscosities of the resulting disperse phase blend homogeneouscompositions, are as shown in Table IX below:

                  TABLE IX                                                        ______________________________________                                        DISPERSE PHASE COMPOSITIONS                                                                   Preferred Approx.                                                                            Preferred Approx.                                   Disperse   Weight Ratio of                                                                              Viscosity Range                                     Phase      Composition A to                                                                             (CPS) of Blended                               I.D. Composition                                                                              Other Composition(s)                                                                         Disperse Phase                                 No.  of         (B or B + C)   Composition.sup.(1)                            ______________________________________                                        1    A + B      85:15 to 80:20 25,000-27,500                                  2    A + C      85:15 to 80:20 30,000-33,000                                  3    A + B + C  70:15:15 to    at least 35,000.sup.(2)                                        80:10:10                                                      ______________________________________                                         Table IX Footnotes                                                            .sup.(1) All viscosities are measured in centipoises at 25° C. wit     a Brookfield viscometer using a No. 4 spindle operating at 20 rpm.            .sup.(2) More preferably, this viscosity is not greater than about 85,000     centipoises (so measured).                                               

The disperse phase compositions are conveniently prepared using simplemechanical blending procedures and conventional mixing apparatus withthe amount of mixing shear force used being at least sufficient toproduce a uniform and homogeneous product blend. As shown in Table IX,the viscosity of a resulting disperse phase composition appears to becharacteristically greater than that of the Composition A that isincorporated therein.

As indicated, preferred disperse phase compositions incorporate allthree of Compositions A, B and C. While such an (A+B+C) composition canbe prepared by any convenient procedure, such as by first blendingtogether Compositions A and B or Compositions A and C, and then furthercombining with the resulting blend a third Composition (eitherComposition C or B, as the case may be), it is presently preferred tofirst mix together Composition A and C in a weight ratio within therange shown in Table IX and then thereafter to mix Composition Btherewith using a weight ratio sufficient to achieve a mixing weightratio as shown in Table IX for all three of Compositions A, B and C.

An (A+B+C) composition characteristically appears to have a viscositythat is greater than either an (A+B) composition or an (A+C)composition. It is theorized, and there is no intent herein to be boundby theory, that the reason for this increase is that the quaternizedcellulose ether has reacted in some now unknown manner with at least onecomponent present in the (A+B+C) composition, perhaps with thepolyurethane polymer, and, if present, the carboxylated crosslinkablepolymer. An (A+B+C) composition, particularly one prepared by theforegoing preferred procedure, appears to have better tack andelasticity characteristics than other such disperse phase compositions.

The (A+B), (A+C) and (A+B+C) disperse phase compositions of the presentinvention all appear to be novel over all known prior art teachingspertaining to multicolor aqueous disperse phase compositions, and tohave higher viscosities than any previously known aqueous pigmentablecomposition of the type usable for the disperse phase in multicolorpaints.

The (A+B), (A+C) and (A+B+C) disperse phase compositions are used tomake multicolor paints of the invention by the following procedure:

First, at least two different (A+B), (A+C) or (A+B+C) compositions areeach prepared, each preferably being made by the preferred proceduredescribed above. Each (A+B), (A+C) and (A+B+C) composition of theplurality is prepared using a differently colored pigment; thus, eachcomposition has a different apparent color. Preferably, all of thecompositions used in any given multicolor paint are of the same type,that is, (A+B), (A+C) and (A+B+C).

Next, the plurality of the different (A+B), (A+C) or (A+B+C)compositions are blended together with a preformed continuous phasecomposition which is comprised of a clear or pigmented vehicle as inComposition D. In general, Composition D used as a continuous phase in amulticolor paint of this invention should have at the time of blendingwith (A+B), (A+C), or (A+B+C) compositions a viscosity that ispreferably in the range of about 3,000 to about 7,000 cps as measured at25° C. with a Brookfield viscometer operating at 20 rpm and using a No.4 spindle. Such viscosity is more preferably in the range of about 5,000to about 6,000 cps. Composition D preferably should have a viscositywhich is less than the viscosity of the starting (A+B), (A+C) or (A+B+C)blends.

In general, the viscosity of the continuous phase is less than theviscosity of the gel phase composition. Preferably, the ratio of theviscosity of the continuous phase composition to the viscosity of eachof the disperse phase compositions (comparably measured) is in the rangeof about 1:5 to about 1:10 with a viscosity ratio range of about 1:7 toabout 1:8.5 being presently more preferred.

The respective amounts of the individual (A+B), (A+C) and (A+B+C)compositions employed in a given multicolor paint can be variedaccording to the artistic preference of the formulator. Preferably, theweight ratio of the total weight of all (A+B), (A+C) and/or (A+B+C)compositions employed in a given multicolor paint of this invention tothe weight of Composition D employed in such paint is in the range ofabout 1:1 to about 6:4, although larger and smaller weight ratios can beused, if desired.

In a product multicolor paint of this invention, such viscositydifferences between the discontinuous phase compositions and thecontinuous phase compositions, and such a total weight ratio of weightof total discontinuous phase compositions to weight of continuous phasecomposition are now believed to be desirable because such appear toresult in production of a product paint wherein the disperse phasebodies form and remain suspended and discrete during subsequent paintstorage.

Disperse phase (A+B), (A+C) and (A+B+C) compositions can be blended witha continuous phase composition in any order or manner. During blending,the disperse phase compositions break up and disperse to formdiscontinuous phase bodies in the continuous phase. The mixing shearforce used in the blending is inversely proportional to the average sizeof the disperse phase bodies formed. The resulting dispersionconstitutes a multicolor paint according to this invention.

The discontinuous phase bodies are characterized by what is believed tobe unusual and surprisingly greater structural integrity compared to thestructural integrity of prior art discontinuous phase bodies, such asthe bodies described, for example, in the above-referenced Sellars etal. U.S. Pat. No. 3,950,283.

A continuous phase which includes a crosslinkable Composition D exhibitssuperior film properties compared to continuous phases of the prior art.

Various mixing procedures can be employed. When, for example, amulticolor paint of this invention is prepared wherein the discontinuousphase color bodies are to have different sizes relative to one another,one can prepare the different sized discontinuous phase bodies inseparate mixing operations with different Composition D batches usingdifferent mixing shear forces. Thereafter, the different and separatelyprepared continuous/discontinuous phase dispersion compositions can beblended together. Preferably a mixing shear force is used in such ablending which is not larger than that used to make the largest sizedisperse phase bodies desired in the resulting mixed dispersions.

Study of the (A+B), (A+C) and (A+B+C) compositions indicates that eachis a gel and remains a gel when formed into disperse phase bodies in amulticolor paint composition of the invention. The gel bodies formedfrom (A+B+C) compositions are believed to have the greatest internalstructural integrity or strength.

(e) Product Multicolor Paint Characteristics

Once the (A+B), (A+C) and (A+B+C) compositions are broken up by mixingin a Composition D to form a multicolor paint composition of thisinvention, the resulting disperse phase bodies apparently cannot and donot separate to reform the respective original (A+B), (A+C) and/or(A+B+C) compositions. Apparently, the disperse phase particles or bodieseach have a crosslinked surface and internal structure, and also aninterfacial bonding relationship between the continuous phase and thediscontinuous phase bodies. No discrete interfacial material layer, suchas a shell wall or the like, is believed to exist between the dispersephase bodies and the continuous phase.

Typically, the disperse phase body particle sizes in a multicolor paintof this invention have a size in the range of about 0.2 to about 15 mm,but larger and smaller body or particle sizes can be employed, ifdesired.

The multicolor paint compositions of this invention are characterized byhaving indefinitely long storage stability, including shelf, shipping,thermal, and vibrational (mixing) aspects.

While a multicolor paint formulation of this inventioncharacteristically contains at least two distinct colors, those skilledin the art will appreciate that a particular multicolor paintformulation may contain many different classes of distinctly separatelycolored or noncolored disperse phase bodies, perhaps six or more, eachindividual identically colored group of discrete disperse phase bodieshaving been separately preliminarily prepared as an (A+B), (A+C) or(A+B+C) disperse phase composition as hereinabove described, before thedisperse phase composition is blended into the continuous phase. Variousratios and proportions of respective (A+B), (A+C) and (A+B+C)compositions relative to one another can be used as desired in blending,as indicated above.

An optional but preferred component of a multicolor paint of thisinvention is a neutralizer base which is used for reasons of pH controland buffering. Examples of suitable neutralizers include aqueouspotassium hydroxide, ammonium hydroxide, triethanolamine,dimethylethanol amine, mixtures thereof, and the like. When employed,the amount of neutralizer used can range from greater than zero up toabout 0.6 weight percent on a 100 weight percent total paint compositionbasis. The neutralizer, when used, can be added at any convenient pointduring the blending sequence; for example, the neutralizer can be addedto Composition A or to the final mixture of gel phase composition andcontinuous phase at the time when such are being blended together. It ispresently preferred to have a product paint composition wherein thecontinuous phase has a pH in the range of about 8 to about 9 andsimilarly for the discontinuous (or disperse) phase. The neutralizer canbe preliminarily prepared as an aqueous solution or dispersion for easein blending.

In a product multicolor paint of this invention, at least one of eitherthe total discontinuous phase or the continuous phase thereof canoptionally contain from and including 0 to about 25 weight percent on a100 weight percent total phase basis of water dispersed, inertfilm-forming carboxylated polymer (as described above) plus sufficientwater dispersed crosslinking agent (as described above) to crosslinkthis carboxylated polymer when the carboxylated polymer and thecrosslinking agent are dried from an aqueous dispersion at roomtemperature. Usually the total amount of this crosslinking polymer inboth phases of a product multicolor paint is not more than about 3weight percent on a total 100 weight percent product paint basis.

The compositional characteristics for a preferred and illustrative classof multicolor paint compositions of this invention (expressed on a totalcomposition basis) are summarized in Table X below:

                  TABLE X                                                         ______________________________________                                        MULTICOLORED PAINT COMPOSITIONS                                                                 Weight Percent                                                                100% Basis.sup.(1)                                                                  Presently Preferred                                                           Most      Range                                       ID   Component          Preferred (About)                                     ______________________________________                                        1    Inert film-forming polymer                                                                       22.5%      8-30%                                           system (Total)                                                           1a   Polyurethane polymer system                                                                      (7%)      (15-30%)                                    1b   Carboxylated polymer system                                                                      (15.5%)    (0-30%)                                    2    Pressure-responsive contact                                                                      20.00%    12-25%                                           adhesive                                                                 3    Hydroxy (alkyl) cellulose                                                                        0.35%      0.3-1.25%                                  4    Pigment            8.0%       2-20%                                      5    Quaternized cellulose ether                                                                      0.15%     0.05-2%                                     6    Colloidal silica   1.2%      0.5-3%                                      7    Clay               3.0%      0.1-10%                                     8    Peptizing agent    0.35%     0.1-1.0%                                    9    Organofunctional silane                                                                          0.01%     0.002-0.015%                                10   Organic cosolvent  7.25%     1.5-7.5%                                    11   Water              39.5%     20-75%                                      12   Wetting agent      0.25%     0.10-0.50%                                  13   Anti-foaming agent 0.15%     0.05-0.50%                                  14   Bonding agent      0.1%      0.05-0.25%                                  15   Neutralizer        0.2%      0.05-0.50%                                       (Total Weight Percent)                                                                           (100.0)   (100.0)                                     ______________________________________                                         Table X Footnote:                                                             .sup.(1) Weight ranges enclosed in parentheses are not included in the 10     weight percent total composition basis since such ranges are associated       with (i.e., are incorporated with) item 1 (the polymer system).          

The excellent strength and stability characteristics of a multicoloredpaint composition of this invention provide a composition which can bebrushed, rolled or sprayed using the relatively high shear forces thatare characteristically exerted upon a paint formulation being so appliedwithout appreciable disperse phase color body breakdown.

It will be appreciated that a multicolor paint composition of thepresent invention can generally be applied by any conventionalapplication method desired utilizing spraying, brushing, roller, pad, orthe like.

As the applied paint coating dries on a surface, the inert film-formingpolyurethane polymer in combination with the other components presentform a continuous film or coating in which the disperse phase bodiesbecome located typically in adjacent but spaced, discrete relationshipto one another. Both the water and the organic cosolvent (if present)evaporate. The resulting coating becomes substantially fullycrosslinked.

It is a surprising feature and an advantage of the present inventionthat, when a paint composition of this invention is applied, forexample, by a roller applicator or the like, to a substrate, the paintcomposition transfers quickly from the applicator to the substrate.Desirable multicolor paint quality characteristics including especiallythe stability characteristics of the disperse phase color bodies are notadversely affected by such a rapid transfer. Indeed, this transferappears to avoid damage to the disperse phase bodies since back andforth applicator stroking against the freshly painted substrate surfaceas in the prior art appears sometimes to induce some damage to thedisperse phase bodies.

It is an additional surprising feature and an advantage of the presentinvention that when a paint composition of this invention has beenapplied to a substrate surface and allowed to dry preferably in ambientair, the resulting multicolored coating displays inert filmcharacteristics and is substantially non-tacky even though thepressure-sensitive adhesive has been incorporated thereinto.

A product dried coating displays excellent properties, such as waterresistance, as well as abrasion (wear) resistance, thermal stability,washability, surface smoothness, and the like.

EMBODIMENTS

The invention is further illustrated by the following Examples.

EXAMPLES 1 and 2 Preparation of First and Second "Composition "A"

Two embodiments of "Composition A" are prepared by blending together thefollowing components in the respective amounts indicated using a Cowlesblade operating at about 450 to about 1500 rpm in a mixer:

                  TABLE XI                                                        ______________________________________                                        FIRST & SECOND "COMPOSITION A"                                                Component            Ex. 1     Ex. 2                                          ______________________________________                                        Dispersed Polyurethane Polymer                                                                     58.17     48.17                                          (QW-18-1)                                                                     Dispersed Carboxylated Polymer                                                                     --        10.00                                          (Pliolite 7103)                                                               Water                27.38     27.38                                          Wetting agent (TAMOL 165)                                                                          0.50      0.50                                           Anti-foaming agent (NOPCO NXZ)                                                                     0.50      0.50                                           Hydroxyethyl cellulose (Cellosize                                                                  1.00      1.00                                           QP-100-MH)                                                                    Titanium dioxide (Dupont R-900)                                                                    10.00     --                                             Bone black (Ebonex 3D)                                                                             --        8.20                                           Barium sulfate (Barytes)                                                                           --        1.80                                           Organo functional silane (A-187)                                                                   0.20      0.20                                           Carbodiimide (UCARLNK XL-25-SE)                                                                    2.00      2.00                                           Ammonium hydroxide (28% Ammonia)                                                                   0.25      0.25                                           (Total Weight Percent)                                                                             (100.00)  (100.00)                                       ______________________________________                                    

In Table XI, the "Composition A" of Example 1 is white in color and itsBrookfield viscosity is believed to be in the range of about 10,000 toabout 25,000 cps measured at 25° C. using a No. 4 spindle operating at20 rpm; and the "Composition A" of Example 2 is black in color and itsBrookfield viscosity is believed to be in the range of about 10,000 toabout 30,000 cps similarly measured.

EXAMPLE 3 Preparation of Clear "Composition A"

A clear "Composition A" is prepared by blending together the followingindicated components in the respective amounts indicated using a Cowlesblade operating at about 450 to about 1500 rpm in a mixer.

                  TABLE XII                                                       ______________________________________                                        CLEAR "COMPOSITION A"                                                         Component                 Ex. 3                                               ______________________________________                                        Dispersed Acrylic Polymer (Pliolite 7103)                                                               66.0                                                Adhesive D                2.00                                                Water                     33.0                                                Wetting agent (TAMOL 165) 0.50                                                Anti-foaming agent (NOPCO NXZ)                                                                          0.50                                                Hydroxyethyl cellulose (Cellosize QP-100-MH)                                                            1.00                                                Silica (OK 412)           2.50                                                Organo functional silane (A-187)                                                                        0.20                                                Carbodiimide (UCARLNK XL-25-SE)                                                                         2.00                                                Ammonium hydroxide (28% Ammonia)                                                                        0.25                                                (Total Weight Percent)    (100.00)                                            ______________________________________                                    

Adhesive D is as identified in Example 6 below.

The "Composition A" of Example 3 is clear and its Brookfield viscosityis believed to be in the range of about 10,000 to about 20,000 cpsmeasured at 25° C. using a No. 4 spindle operating at 20 rpm.

EXAMPLE 4 Preparation of "Composition B"

A "Composition B" is prepared by blending together the followingcomponents in the respective amounts indicated using a Cowles bladeoperating at about 1000 to about 2500 rpm in a mixer:

                  TABLE XIII                                                      ______________________________________                                        COMPOSITION B                                                                 ______________________________________                                        Water                     98.00                                               Quaternized cellulose ether                                                                              2.00                                               Polyquaternium-10 (UCARE Polymer JR-30)                                       (Total Weight Percent)    (100.00)                                            ______________________________________                                    

The Brookfield viscosity of the resulting "Composition B" is about50,000 cps measured at 25° C. using a No. 4 spindle operating at 20 rpm.

EXAMPLE 5 Preparation of "Composition C"

A "Composition C" is prepared by blending together the followingcomponents in the respective amounts indicated using a Cowles bladeoperating at about 750 to about 2000 rpm in a mixer:

                  TABLE XIV                                                       ______________________________________                                        COMPOSITION C                                                                 ______________________________________                                        Water                    89.40                                                Synthetic sodium magnesium lithium                                                                     9.50                                                 hectorite clay (Laponite RDS)                                                 Peptizing agent (tetrasodium pyrophosphate)                                                            1.10                                                 (Total Weight Percent)   (100.00)                                             ______________________________________                                    

The Brookfield viscosity of the resulting "Composition C" is about85,000 cps measured at 25° C. using a No. 4 spindle operating at 20 rpm.

EXAMPLE 6 Preparation of "Composition D"

Various different "Compositions D" are prepared which are, respectively,clear, pigmented, metallic or dyed with a transparent dye. Thesecomponents are prepared by blending together the following components inthe respective amounts indicated using a Cowles blade operating at about750 to about 1,500 rpm in a mixer.

The same water dispersible, film-forming, crosslinkable polyurethanepolymer that is employed in the discontinuous phase (see Examples 1 and2 of Composition A) is preferably used in preparing "Composition D"(i.e., QW18-1). The addition of such a polymer to a "Composition D" thatcontains an adhesive results in a multicolor paint that has a moreimpregnable film with a higher solids content and better hidingproperties relative to a paint which includes a corresponding"Composition D" that is formed as taught in Ser. No. 851,525.

The use of the foregoing polymers in a "Composition D" that isincorporated into a multicolor paint with an adhesive also provides amore homogeneous paint film which improves the drying speed, the sheencontrol, washability, durability and water resistance of the finalcoating. When the foregoing polymer is crosslinked, a high degree ofhardness, mar resistance, chemical resistance and thermal stability isprovided. The resulting multicolor paint can be rapidly applied as asurface coating with a paint roller or brush and can be sprayed withspray equipment.

Various Composition D formulations are shown in Table XV below (allquantities are expressed on a 100 weight percent total compositionbasis):

                  TABLE XV                                                        ______________________________________                                        COMPOSITION D EXAMPLES                                                                                           Trans-                                                                        parent                                            Clear   Pigmented Metallic  Dye                                               Ex. 6a  Ex. 6b    Ex. 6c    Ex. 6d                                     ______________________________________                                        Polyurethane                                                                           15.07     15.07     23.57   16.07                                    Polymer                                                                       Carboxylated                                                                           2.00      2.00                                                       Polymer                                                                       Adhesive A                                                                             20.00                                                                Adhesive B         20.00                                                      Adhesive C                   20.00                                            Adhesive D                           20.00                                    Adhesive E                                                                             10.00                                                                Adhesive F                           10.00                                    Water    44.70     44.70     44.70   44.70                                    Clay     4.75      4.75      4.75    4.75                                     Peptizing                                                                              0.55      0.55      0.55    0.55                                     agent                                                                         Anti-foaming                                                                           0.15      0.15      0.15    0.15                                     agent                                                                         (NOPCO                                                                        NXZ)                                                                          Wetting agent                                                                          0.15      0.15      0.15    0.15                                     (TAMOL                                                                        165)                                                                          Silica   2.50      2.50      2.50    2.50                                     (OK412)                                                                       Organo   0.13      0.13      0.13    0.13                                     functional                                                                    silane (A-187)                                                                Titanium --        10.00     --      --                                       dioxide                                                                       (Dupont                                                                       R-900)                                                                        Water mis-                                                                             --        --        2.50    --                                       cible alu-                                                                    minum paste                                                                   (Staphydro-                                                                   Lac                                                                           W-60-NL)                                                                      Organic  --        --        1.00    --                                       cosolvent                                                                     (Butyl                                                                        Cellosolve)                                                                   Water mis-                                                                             --        --        --      1.00                                     cible dye                                                                     (NEROSOL                                                                      Yellow R)                                                                     (Total   (100.00)  (100.00)  (100.00)                                                                              (100.00)                                 Weight                                                                        Percent)                                                                      ______________________________________                                    

In the foregoing Table, "Adhesive A" comprises "Robond PS-20" which is atrademark of Rohm and Haas Company, Philadelphia, Pa. for an aqueousacrylic pressure-sensitive adhesive which has a milky white appearance,a solids content of about 53% on a 100 weight percent total compositionbasis and a pH of about 9.0 to 9.5. This adhesive is film-forming and ischaracterized by relatively low peel adhesion and tack, but has highshear resistance.

"Adhesive B" in the foregoing Table comprises a mixture of "RobondPS-20" with "Luhydran A-848-S" in a 4:1 weight ratio. "Luhydran A-848-S"is a trademark of BASF Corporation Chemicals Division, Parsippany, N.J.for an aqueous milky white methacrylic acid ester polymer dispersionwhich contain about 40 weight percent of this polymer with the balanceup to 100 weight percent being water, and which has a pH of about 7.5.This adhesive is film-forming and is useful as a binder in water basedcoatings.

"Adhesive C" in the foregoing Table comprises "Robond PS-83-D" which isa trademark of the Rohm and Haas Company for an aqueous acrylicpressure-sensitive adhesive copolymer which has a milky-whiteappearance, a solids content of about 53% on a 100 weight percent totalcomposition basis and a pH of about 9.1 to 9.8. This adhesiveincorporates as one major monomer butyl acrylate. This adhesive isfilm-forming and displays a balance of peel adhesion, quick stick andshear resistance.

"Adhesive D" in the foregoing Table comprises "Robond PS-83-D" and"Luhydran A-848-S" in a 4:1 weight ratio.

"Adhesive E" in the foregoing Table comprises "QThane LQW 10-207" whichis a trademark of the K. J. Quinn & Company, Inc. for a translucentaliphatic single component water based polyurethane dispersion withadhesive properties and green strength. The dispersion contains about 40weight percent solids with the balance up to 100 weight percent beingwater and the dispersion has a pH of about 7.5. The dispersion and itspolymer may be further crosslinked with aziridines.

"Adhesive F" in the foregoing Table comprises "QThane" LQW10-207" and"Luhydran A-848-S" in a 4:1 weight ratio.

The Brookfield viscosity of each resulting above "Composition D" ofTable XV is in the range of about 1,000 to about 1,500 cps measured at25° C. using a No. 4 spindle operating at 20 rpm.

EXAMPLE 7 Preparation of First Disperse Phase Gel Composition

A first disperse phase gel composition is prepared by blending togetherthe following indicated amounts of each of Examples 1 and 4 using aCowles blade operating at about 800 to about 1500 rpm in a mixer:

    ______________________________________                                        "Composition A" Example 1 (white)                                                                     .sup.  82.40 wt %                                     "Composition B" Example 4                                                                             .sup.  17.60 wt %                                     (Total Weight Percent)  (100.00)                                              ______________________________________                                    

The Brookfield viscosity of the resulting gel composition is about26,000 cps measured at 25° C. using a No. 4 spindle operating at 20 rpm.

EXAMPLE 8 Preparation of First Disperse Phase Gel Composition

A first disperse phase gel composition is prepared by blending togetherthe following indicated amounts of each of Examples 1 and 5 using aCowles blade operating at about 1000 to about 2000 rpm in a mixer:

    ______________________________________                                        "Composition A" Example 1 (white)                                                                     .sup.  82.40 wt %                                     "Composition C" Example 5                                                                             .sup.  17.60 wt %                                     (Total Weight Percent)  (100.00)                                              ______________________________________                                    

The Brookfield viscosity of the resulting gel composition is about31,000 cps measured at 25° C. using a No. 4 spindle operating at 20 rpm.

EXAMPLE 9 Preparation of First Disperse Phase Gel Composition

A first disperse phase gel composition is prepared by blending togetherthe following indicated amounts of each of Examples 1, 4 and 5 using aCowles blade operating at about 1000 to about 2500 rpm in a mixer:

    ______________________________________                                        "Composition A" Example 1 (white)                                                                     .sup.  70.00 wt %                                     "Composition B" Example 4                                                                             .sup.  15.00 wt %                                     "Composition C" Example 5                                                                             .sup.  15.00 wt %                                     (Total Weight Percent)  (100.00)                                              ______________________________________                                    

The Brookfield viscosity of the resulting gel composition is about35,000 cps measured at 25° C. using a No. 4 spindle operating at 20 rpm.

EXAMPLE 10 Preparation of Second Disperse Phase Gel Composition

A second disperse phase gel composition is prepared by blending togetherthe following indicated amounts of each of Examples 2 and 4 using aCowles blade operating at about 800 to 1500 rpm in a mixer:

    ______________________________________                                        "Composition A" Example 2 (black)                                                                     .sup. 82.40 wt %                                      "Composition B" Example 4                                                                             .sup. 17.60 wt %                                      (Total Weight Percent)  (100.00)                                              ______________________________________                                    

The Brookfield viscosity of the resulting gel composition is about29,500 cps measured at 25° C. using a No. 4 spindle operating at 20 rpm.

EXAMPLE 11 Preparation of Second Disperse Phase Gel Composition

A second disperse phase gel composition is prepared by blending togetherthe following indicated amounts of each of Examples 2 and 5 using aCowles blade operating at about 1000 to about 2000 rpm in a mixer:

    ______________________________________                                        "Composition A" Example 2 (black)                                                                     .sup.  82.40 wt %                                     "Composition C" Example 5                                                                             .sup.  17.60 wt %                                     (Total Weight Percent)  (100.00)                                              ______________________________________                                    

The Brookfield viscosity of the resulting gel composition is about32,000 cps measured at 25° C. using a No. spindle operating at 20 rpm.

EXAMPLE 12 Preparation of Second Disperse Phase Gel Composition

A second disperse phase gel composition is prepared by blending togetherthe following indicated amounts of each of Examples 2, 4 and 5 using aCowles blade operating at about 1000 to about 2500 rpm in a mixer:

    ______________________________________                                        "Composition A" Example 2 (black)                                                                     .sup.  70.00 wt %                                     "Composition B" Example 4                                                                             .sup.  15.00 wt %                                     "Composition C" Example 5                                                                             .sup.  15.00 wt %                                     (Total Weight Percent)  (100.00)                                              ______________________________________                                    

The Brookfield viscosity of the resulting gel composition is about37,500 cps measured at 25° C. using a No. spindle operating at 20 rpm.

EXAMPLE 13 Preparation of Third Disperse Phase Gel

A clear third disperse phase gel composition is prepared by blendingtogether the following indicated amounts of each using a Cowles bladeoperating at about 1,000 to about 2,500 rpm in a mixer:

    ______________________________________                                        "Composition A" Example 3                                                                             .sup.  70.00 wt %                                     "Composition B" Example 4                                                                             .sup.  15.00 wt %                                     "Composition C" Example 5                                                                             .sup.  15.00 wt %                                     (Total Weight Percent)  (100.00)                                              ______________________________________                                    

The Brookfield viscosity of the resulting clear gel composition is about35,000 cps measured at 25° C. using a No. 4 spindle operating at 20 rpm.

EXAMPLES 14-17 Preparation of Multicolor Paint Including Composition Das the Continuous Phase

Multicolor paints are prepared by mixing the quantity of Composition Dshown in the following Table XVI with each of the respective specifiedpreviously described and prepared intermediate composition. Allcomponents for each paint are expressed on a 100 weight percent totalcomposition basis.

                  TABLE XVI                                                       ______________________________________                                                                    Ex. 16                                                         Ex. 14         Trans-   Ex. 17                                                White Ex. 15   parent   Black                                                 &     Black    Yellow   &                                                     Black Metallic Metallic White                                    ______________________________________                                        Composition D clear                                                                          --      --       --     46.60                                  (Ex. 6a)                                                                      Composition D pigmented                                                                      46.60   --       --     --                                     (Ex. 6b)                                                                      Composition D metallic                                                                       --      22.80    --     --                                     (Ex. 6c)                                                                      Composition D transparent                                                                    --      --       22.80  --                                     dye (Ex. 6d)                                                                  First disperse phase gel                                                                     46.60   --       --     46.60                                  (white)                                                                       Examples 7, 8 and 9                                                           Second disperse phase gel                                                                    --      --       --     46.60                                  (black)                                                                       Examples 10, 11 and 12                                                        Third disperse phase gel                                                                     --      22.80    22.80                                         (clear) Example 13                                                            Composition D clear                                                                           1.20   25.00    --      1.20                                  (Ex. 6a)                                                                      Composition D pigmented                                                                      --      --       --     --                                     (Ex. 6b)                                                                      Composition D metallic                                                                       --      --       25.00  --                                     (Ex. 6c)                                                                      Composition D transparent                                                                    --      --       --     --                                     dye (Ex. 6d)                                                                  First disperse phase gel                                                                     --      --       --     --                                     (white)                                                                       Examples 7, 8 and 9                                                           Second disperse phase gel                                                                     1.20   25.00    --      1.20                                  (black)                                                                       Examples 10, 11 and 12                                                        Third disperse phase gel                                                                     --      --       25.00  --                                     (clear) Example 13                                                            Butyl benzyl phthalate                                                                        1.00    1.00     1.00   1.00                                  (Santicizer 160)                                                              Ester Alcohol   1.00    1.00     1.00   1.00                                  (TEXANOL)                                                                     Ethylene glycol butyl                                                                         2.40    2.40     2.40   2.40                                  ether (Butyl Cellosolve)                                                      ______________________________________                                    

Throughout the preparation of the multicolor paints of Examples 14-17, aCowles blade in a mixer operates in the range of about 400 to about 500rpm. The Brookfield viscosity of the product multicolor paint is in therange of about 5,000 to about 7,000 cps measured at 25° C. using a No. 4spindle operating at 20 rpm.

The foregoing multicolor paints exhibit the improved propertiesdiscussed above with reference to Example 6. The paint can be applied asa surface coating with a paint roller or brush and can be sprayed withspray equipment as described below.

EXAMPLE 18 Application of the Multicolor Paint

Each of the multicolor paints of the Examples 14-17 is applied usingeach of:

(1) roller application using a foam roller at 30-60 pps (pores persquare inch);

(2) brush application using a foam, synthetic or bristle type brush;

(3) a conventional air spray set up with a pressurized feed tank anddual regulators. Binks Gun Model 2001 with an internal or external mixair nozzle assembly. Air pressures with an internal mix assembly: gunpressure, 30 psi and material air pressure 35 psi. With external mixnozzle assembly, air pressure at the gun is about 20 to 30 about psi andair pressure of the material is about 10 to about 15 psi;

(4) most airless sprayers. Pump type Graco Model PT2500 with 221-517 tipsize and using application pressures of about 200 psi at the gun tip;and

(5) H.V.L.P. spray equipment (high volume, low pressure). (Wagner CapSpray Units CS5000 and CS8000).

It is found that a uniform multicolor coating is produced from eachpaint. This coating is applied rapidly from the roller and the brush.Each coating dries to a tack-free film (or coating) in about 30 minutesin air. Maximum inert film properties are attainable after an additionalpost-curing time of about 96 hours in air.

Each fully cured coating is found to pass the ASTM No. D-1308-79 waterspot test, both opened and covered.

Drying time of a coated paint can be accelerated by forced air drying at125°-150° F.

EXAMPLES 19 THROUGH 34 Other Embodiments

When each of the water soluble, inert film-forming, crosslinkablepolyurethane polymeric dispersions shown in Table XVI below issubstituted for the polyurethane polymer employed in Examples 1 and 2,and then when each of such resulting "Compositions A" is used to preparemulticolor paints as described in the procedures of foregoing Examples,a multicolor paint is produced which, when coated as described inExample 18, is found to pass the water spot tests of ASTM D-1308-79. Allcomponents for each paint are expressed on a 100 weight percent totalcomposition basis.

                                      TABLE XVII                                  __________________________________________________________________________                 Other Embodiments Using Crosslinkable Water Soluble                           Polymers                                                                      Example No.                                                                   19   20   21   22   23   24   25   26   27   28                  __________________________________________________________________________    Water        37.85                                                                              37.85                                                                              42.02                                                                              50.76                                                                              42.02                                                                              41.95                                                                              37.85                                                                              45.35                                                                              42.85                                                                              42.85               Wetting agent                                                                              0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50                (TAMOL 165)                                                                   Anti-foaming agent                                                                         0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20                (NOPCO NXZ)                                                                   Hydroxyethyl cellulose                                                                     1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 --   --                  (Cellosize QP-100-MH)                                                         Titanium dioxide                                                                           10.00                                                                              10.00                                                                              10.00                                                                              10.00                                                                              10.00                                                                              10.00                                                                              10.00                                                                              10.00                                                                              10.00                                                                              10.00               (Dupont R-900)                                                                Polyurethane dispersion                                                       Aliphatic QW-10                                                                            37.50                                                            Aliphatic QW-12   37.50                                                       Aliphatic QW-14        33.33                                                  Aliphatic QW-16             24.59                                             Sancure 815                      33.33                                        Sancure 878                           33.40                                   Sancure 849                                37.50                              Sancure 895                                     30.00                         Sancure 899                                                                   Waterborne aliphatic                                 40.00                                                                              --                  urethane "Sancure" 898                                                        Waterborne aliphatic                                 --   40.00               urethane "Q-Thane" QW-18                                                      Butyl benzyl phthalate                                                                     1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 --   --                  (Santicizer 160)                                                              Organo functional silane                                                                   0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20                (A-187)                                                                       Ester alcohol                                                                              1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 --   --                  (TEXANOL)                                                                     Ethylene glycol butyl                                                                      3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50 --   --                  ether (Butyl Cellosolve)                                                      Carbodiimide 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00                (UCARLNK XL-25-SE)                                                            Ammonium hydroxide                                                                         0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.25 0.25                (28% Ammonia)                                                                 (Total Weight Percent)                                                                     (100.00)                                                                           (100.00)                                                                           (100.00)                                                                           (100.00)                                                                           (100.00)                                                                           (100.00)                                                                           (100.00)                                                                           (100.00)                                                                           (100.00)                                                                           (100.00)            __________________________________________________________________________                                                              1                                         Other Embodiments Using Crosslinkabled Water                                  Soluble Polymers                                                              Example No.                                                                   29     30     31     32    33     34                    __________________________________________________________________________    Water                 35.85  35.85  35.85  35.85 35.85  35.85                 Wetting agent (TAMOL 165)                                                                           0.50   0.50   0.50   0.50  0.50   0.50                  Anti-foaming agent (NOPCO NXZ)                                                                      0.20   0.20   0.20   0.20  0.20   0.20                  Hydroxyethyl cellulose                                                                              1.00   1.00   1.00   1.00  1.00   1.00                  (Cellosize QP-100-MH)                                                         Titanium dioxide (Dupont R-900)                                                                     10.00  10.00  10.00  10.00 10.00  10.00                 Adhesive A (Robond PS20)                                                                            20.00                                                   Adhesive B (PS-20 with A-848-S)                                                                            20.00                                            Adhesive C (Robond PS-83-D)         20.00                                     Adhesive D (Robond PS83D with A-848-S)     20.00                              Adhesive E (Qthane LQW 10-207)                   20.00                        Adhesive F (Qthane LQW 10-207 with                      20.00                 A-848-S)                                                                      Aliphatic urethane (Q-thane QW-18)                                                                  20.00  20.00  20.00  20.00 20.00  20.00                 Butyl benzyl phthalate (Santicizer 160)                                                             1.50   1.50   1.50   1.50  1.50   1.50                  Organo functional silane (A-187)                                                                    0.20   0.20   0.20   0.20  0.20   0.20                  Ester alcohol (TEXANOL)                                                                             1.25   1.25   1.25   1.25  1.25   1.25                  Ethylene glycol butyl ether                                                                         3.00   3.00   3.00   3.00  3.00   3.00                  (Butyl Cellosolve)                                                            Carbodiimide (UCARLNK XL-25-SE)                                                                     6.00   6.00   6.00   6.00  6.00   6.00                  Ammonium hydroxide (28% Ammonia)                                                                    0.50   0.50   0.50   0.50  0.50   0.50                  (Total Weight Percent)                                                                              (100.00)                                                                             (100.00)                                                                             (100.00)                                                                             (100.00)                                                                            (100.00)                                                                             (100.00)              __________________________________________________________________________

In the foregoing Examples, the hydroxyethyl cellulose can be replacedwith: A) hydroxymethyl cellulose (Dow A type); B) hydroxypropylcellulose (Aqualon Klucel S97A type); and C) sodium carboxy methylcellulose (Aqualon CMC-7-7H3SF). The carbodiimide crosslinker can bereplaced by the polyfunctional aziridine crosslinking agent "Zama-7"from Virginia chemicals. The "Composition C" hectorite clay (LaponiteRDS) can be replaced by: A) Laponite RD; B) Veegum T; and C) Macaloid.And the "Composition C" peptizing agent (tetrasodium pyrophosphate) canbe replaced by: A) sodium pyrophosphate; B) sodium tripolyphosphate; andC) sodium hexametaphosphate.

While the foregoing description makes use of illustrative examples ofvarious types, no limitations upon the present invention are to beimplied or inferred therefrom.

What is claimed is:
 1. A method, for making a water-in-water multicolorpaint having a discontinuous aqueous phase dispersed in a continuousaqueous phase, said method comprising the steps of:(A) providing a firstcomposition comprising on a 100 weight percent basis:(a) about 10 toabout 40 weight percent of a water dispersed, film-forming,crosslinkable, polymer system selected from the group consisting of apolyurethane polymer system, a carboxylated polymer system and mixturesthereof, said polyurethane polymer system comprising on a 100 weightpercent total crosslinkable solids basis about 75 to and including 100weight percent of polyurethane polymer and correspondingly from andincluding 0 to about 25 weight percent of reactive curative, and saidcarboxylated polymer system comprising on a 100 weight percent totalpolymer solids basis about 75 to and including 100 weight percentcarboxylated polymer and correspondingly from and including 0 up toabout 25 weight percent of organic crosslinking agent; (b) about 0.5 toabout 2 weight percent dissolved cellulose material selected from theclass consisting of hydroxy (lower alkyl) cellulose and alkali metalcarboxylated (lower alkyl) cellulose, (c) from and including 0 to about10 weight percent of water dispersed, film-forming, crosslinkablepressure-sensitive contact adhesive selected from the group consistingof polyurethanes and acrylic polymers, (d) from and including 0 to about30 weight percent dispersed pigment, (e) from and including 0 to about10 weight percent organic cosolvent, and (f) about 20 to about 80 weightpercent water; (B) providing a second composition comprising on a 100weight percent basis:(a) about 0.5 to about 5 weight percent dissolvedcationic quaternized cellulose ether, and (b) about 95 to about 99.5weight percent water; (C) providing a third composition comprising on a100 weight percent basis:(a) about 0.5 to about 2 weight percentdissolved peptizing agent, (b) about 5 to about 10 weight percentdispersed water swellable clay, and (c) about 88 to about 95 weightpercent water; (D) providing a fourth composition comprising on a 100weight percent basis:(a) about 5 to about 40 weight percent of saidwater dispersed, film-forming, crosslinkable polymer system, (b) fromand including 0 to about 30 weight percent of a water dispersed,film-forming, crosslinkable pressure-sensitive contact adhesive selectedfrom the group consisting of polyurethanes and acrylic polymers, (c)about 1.5 to about 5 weight percent of said dispersed water swellableclay, (d) about 0.1 to about 0.8 weight percent of said dissolvedpeptizing agent, (e) from and including 0 to about 30 weight percent ofpigment, (f) from and including 0 to about 0.25 weight percent ofanti-foaming agent, (g) from and including 0 to about 0.25 weightpercent of a wetting agent, (h) from and including 0 to about 0.25weight percent of an organofunctional silane, (i) from and including 0to about 5 weight percent of colloidal silica, (j) from and including 0to about 15 weight percent of an organic cosolvent, and (k) about 30 toabout 70 weight percent water,the relationship between components ofsaid fourth composition being such that said fourth composition has aviscosity in the range of about 1,000 to about 1,500 centipoises; (E)blending said first composition with a composition selected from thegroup consisting of:(a) said second composition in the weight ratiorange of about 85:15 through about 80:20 of said first composition tosaid second composition, (b) said third composition in the weight ratiorange of about 85:15 to about 80:20 of said first composition to saidthird composition, and (c) a composition of said second composition andsaid third composition in the weight ratio range of about 70:15:15 toabout 80:10:10 of said first composition to said second composition tosaid third composition so as to produce a first disperse phase gelcomposition having a viscosity in the range of about 25,000 to about85,000 centipoises; and (F) mixing said first disperse phase gelcomposition with said fourth composition with said adhesive beingpresent in at least one of said first compositions or said fourthcomposition the ratio of the viscosity of said fourth composition to theviscosity of said first disperse phase composition being in the range ofabout 1:5 to about 1:10, the mixing shear force used in said mixingbeing sufficient to break up said first disperse phase gel compositioninto discrete gel bodies thereby forming said discontinuous aqueousphase which is dispersed in said fourth composition as said continuousaqueous phase, said mixing shear force being inversely proportional theaverage size of said so formed disperse phase bodies, thereby to producesaid multicolor paint.
 2. The method of claim 1 wherein said inertfilm-forming polymer system comprises a water dispersed polyurethanepolymer system which is:(a) comprised of polyurethane polymer moleculesproduced by polymerizing mainly monomers which are characterized bycontaining at least three functional groups per monomer, and whereinsaid functional groups are selected from the group consisting ofisocyanato, hydroxyl, primary amino and secondary amino, and (b) selfcrosslinkable when dried from an aqueous dispersion of ambienttemperatures, and wherein said pressure-sensitive adhesive comprises apolyurethane.
 3. The method of claim 1 wherein said adhesive is selectedfrom the group consisting of acrylic polymers having a butyl acrylatebackbone and aliphatic polyurethane polymers having a polyetherbackbone.
 4. The method of claim 1 wherein said adhesive comprises awater dispersed acrylic adhesive having a butyl acrylate backbone. 5.The method of claim 1 wherein said adhesive comprises an aliphaticpolyurethane polymer having a polyether backbone.
 6. The method of claim2 wherein each said polyurethane polymer has unreacted but reactablefunctional groups andat least some of said groups are carboxyl groups,and the remainder of said groups are selected from the group consistingof isocyanato, hydroxyl, primary amino, and secondary amino, and whereinsaid reactive curative is water dispersed and is selected from the groupconsisting of polyisocyanates, multifunctional epoxy resins,multifunctional carbodiimides water dispersible polyfunctionalaziridines, and mixtures thereof.
 7. The method of claim 1 wherein saidwater dispersed inert film-forming polymer system comprises a waterdispersed polyurethane polymer which is:(a) characterized by containinga plurality of terminal isocyanato groups per molecule which are eachblocked by an associated blocking agent, and said blocking agent isthermally released from substantially all its associated respectiveisocyanato groups at a temperature in the range of about 50° to about150° C., and (b) crosslinkable when dried from an aqueous dispersion andsaid blocking agent is so thermally released at said temperature.
 8. Themethod of claim 1 wherein, when in said water dispersed inertfilm-forming polymer system said carboxylated polymer system is present,said carboxylated polymer system:(a) is substantially free from urethanelinkages and urea linkages and also is substantially free fromfunctional groups selected from the class consisting of hydroxyl, amino,and isocyanato, and (b) contains at least sufficient water dispersedcrosslinking agent selected from the group consisting of multifunctionalcarbodiimides and polyfunctional aziridines to crosslink saidcarboxylated polymer when said carboxylated polymer and saidcrosslinking agent are dried from an aqueous dispersion at roomtemperatures.
 9. The method of claim 1 wherein in said firstcomposition, said water dispersed, inert film-forming polymer system iscomprised of said carboxylated polymer system.
 10. The method of claim 1wherein in said fourth composition said water dispersed, inertfilm-forming polymer system is comprised of said polyurethane polymersystem.
 11. The method of claim 1 wherein said step (E) is repeated aplurality of times, and each one of the resulting so produced pluralityof disperse phase gel compositions has a different color relation toothers thereof, and each one of said resulting disperse phase gelcompositions is so mixed with said fourth composition.
 12. The method ofclaim 11 wherein the weight ratio of the total weight of said dispersephase gel compositions to the weight of said fourth composition is inthe range of about 1:1 to about 6:4.
 13. The method of claim 11 whereineach of said disperse phase gel compositions has a viscosity which isabout 7 to about 8.5 times greater than the viscosity of said fourthcomposition.
 14. The method of claim 1 wherein said step (E) said firstcomposition is so blended with said combination of said secondcomposition and said third composition to produce said first dispersephase gel composition.
 15. The method of claim 1 wherein a seconddisperse phase gel composition is prepared by said steps (A) through (C)and (E), said second disperse phase composition contains a pigment whichresults in a different coloration for said second disperse phase gelcomposition relative to said first disperse phase gel composition andsaid second disperse phase composition is likewise additionally mixedwith said fourth composition as prepared by said step (D) and broken upinto discrete gel bodies using a mixing procedure as described in saidstep (F), thereby to produce a multicolor water-in-water paint.
 16. Themethod of claim 15 wherein a plurality of further disperse phase gelcompositions are prepared each by said steps (A) through (C) and (E),each of said further disperse phase gel compositions contains a pigmentwhich is different from all others of said disperse phase gelcompositions, and each of said further disperse phase compositions ismixed with said fourth composition and broken up into discrete gelbodies using a mixing procedure as described in said step (F), therebyto produce a multicolor water-in-water paint.
 17. A water-in-watermulticolor paint comprising a discontinuous aqueous phase dispersed in acontinuous aqueous phase,said discontinuous aqueous phase beingcomprised of a plurality of discrete gel bodies, such gel bodies beingcomprised of a uniform aqueous composition containing in admixture:awater dispersed, inert film-forming, crosslinkable polymer systemselected from the group consisting of a polyurethane polymer system, acarboxylated polymer system and mixtures thereof, said polyurethanepolymer system comprising on a 100 weight percent total polymer solidsbasis about 75 to and including 100 weight percent of polyurethanepolymer and correspondingly from and including 0 up to about 25 weightpercent of reactive curative, and said carboxylated polymer systemcomprising on a 100 weight percent total polymer solids basis about 75to and including 100 weight percent carboxylated polymer andcorrespondingly from and including 0 up to about 25 weight percent oforganic crosslinking agent; cellulose material selected from the classconsisting of hydroxy (lower alkyl) cellulose and alkali metalcarboxylated (lower alkyl) cellulose; and at least one gel formerselected from the class consisting of quaternized ethyl cellulose, andincorporating a preformed water dispersed gel comprised of waterswellable clay, peptizing agent and water; said continuous aqueous phasebeing a preformed gel comprised of said water dispersed, inertfilm-forming, crosslinkable polymer system, said water swellable clay,said peptizing agent and water, the viscosity of said continuous phasebeing less than the viscosity of said discontinuous phase, said waterdispersed, film-forming, crosslinkable polymer system comprising in saidcontinuous aqueous phase on a 100 weight percent total polymer solidsbasis about 75 to and including 100 weight percent of said polyurethanepolymer system and correspondingly from and including 0 up to about 25weight percent of said carboxylated polymer system; at least one of saiddiscontinuous aqueous phase and said continuous aqueous phase containinga water dispersed, film-forming crosslinkable pressure-responsivecontact adhesive that is selected from the group consisting ofpolyurethanes and acrylic polymers; said multicolor paint having beenprepared by the method of claim
 1. 18. The multicolor paint of claim 17wherein the total amount of said adhesive in said paint ranges fromabout 5 to about 30 weight percent and wherein said continuous phasecontains no more than about 10 weight percent of said adhesive and saidcontinuous phase contains no more than about 30 weight percent of saidadhesive.
 19. The multicolor paint of claim 17 wherein said inertfilm-forming polymer system comprises a water dispersed polyurethanepolymer system which is:(a) comprised of polyurethane polymer moleculesproduced by polymerizing mainly monomers which are characterized bycontaining at least three functional groups per monomer, and whereinsaid functional groups are selected from the group consisting ofisocyanato, hydroxyl, primary amino and secondary amino, and (b) selfcrosslinkable when dried from an aqueous dispersion at ambienttemperatures, and wherein said pressure-sensitive adhesive comprises apolyurethane.
 20. The multicolor paint of claim 17 wherein said adhesiveis selected from the group consisting of acrylic polymers having a butylacrylate backbone and aliphatic polyurethane polymers having a polyetherbackbone.
 21. The multicolor paint of claim 17 wherein said adhesivecomprises a water dispersed acrylic adhesive having a butyl acrylatebackbone.
 22. The multicolor paint of claim 17 wherein said adhesivecomprises an aliphatic polyurethane polymer having a polyether backbone.23. The multicolor paint of claim 17 wherein said inert film-formingpolymer system comprises a polyurethane polymer system which is:(a)characterized by containing a plurality of terminal isocyanato groupsper molecule which are each blocked by an associated blocking agent, andsaid blocking agent is thermally released from substantially all itsassociated respective isocyanato groups at a temperature in the range ofabout 50° to about 150° C.; and (b) crosslinkable when dried from anaqueous dispersion and said blocking agent is so thermally released atsaid temperature.
 24. The multicolor paint of claim 17 wherein, when insaid water dispersed, inert film-forming, polymer system saidcarboxylated polymer system is present, said carboxylated polymersystem:(a) is substantially free from urethane linkages and urealinkages and also is substantially free from functional groups selectedfrom the class consisting of hydroxyl, amino, and isocyanato, and (b)contains sufficient water dispersed crosslinking agent selected from thegroup consisting of multifunctional carbodiimides and polyfunctionalaziridines to crosslink said carboxylated polymer when said carboxylatedpolymer and said crosslinking agent are dried from an aqueous dispersionat room temperatures.
 25. The multicolor paint of claim 17 wherein, insaid discontinuous phase, said inert film-forming polymer system iscomprised of said carboxylated polymer system.
 26. The multicolor paintof claim 17 wherein, in said continuous phase, said inert film-formingpolymer system is comprised of said polyurethane polymer system.
 27. Themulticolor paint of claim 17 wherein said adhesive is contacted in saidcontinuous phase.
 28. The multicolor paint of claim 17 wherein saidadhesive is contained in both said continuous phase and saiddiscontinuous phase.
 29. The multicolor paint of claim 17 wherein saidadhesive is contained in said discontinuous phase.
 30. The multicolorpaint of claim 17 wherein said discontinuous phase is comprised of atleast two different classes of discrete gel bodies which respectiveclasses differ from each other in color.
 31. The multicolor paint ofclaim 17 wherein the weight ratio of said discontinuous aqueous phase tosaid continuous aqueous phase is in the range of about 1:1 to about 6:4.32. The multicolor paint of claim 17 wherein said discontinuous aqueousphase has an average viscosity which is about 7 to about 8.5 timesgreater than the viscosity of said continuous aqueous phase.
 33. Acoating produced by applying a continuous layer of a multicolor paint ofclaim 17 to a surface and then drying said so applied layer.
 34. Acoating produced by applying a continuous layer of a multicolor paint ofclaim 32 to a surface and then drying said so applied layer.